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In a knowledge-based society, a firm’s intellectual capital represents the wealth of ideas and ability to innovate, which are indispensable elements for the future growth. Therefore, the intellectual capital is evidently recognized as the most valuable asset in the organization. Considered as intangible asset, intellectual capital is the basis based on which firms can foster their sustainable competitive advantage. One of the essential components of the intellectual capital is a social capital, indicating the firm’s individual members’ ability to build a firm’s social networks. As such, social capital is a powerful concept necessary for understanding the emergence, growth, and functioning of network linkages. The more social capital a firm is equipped with, the more successfully it can establish new social networks. By providing a shared context for social interactions, social capital facilitates the creation of new linkages in the organizational setting.This concept of “person-environment fit” has long been prevalent in the management literature. The fit is grounded in the interaction theory of behavior. The interaction perspective has a fairly long theoretical tradition, beginning with proposition that behavior is a function of the person and environment. This view asserts that neither personal characteristics nor the situation alone adequately explains the variance in behav-ioral and attitudinal variables. Instead, the interaction of personal and situational variables accounts for the greatest variance. Accordingly, the person-environment fit is defined as the degree of congruence or match between personal and situational variables in producing significant selected outcomes.In addition, information systems acceptance factors enable organizations to build large electronic commun-ities with huge knowledge resources. For example, the Intranet helps to build knowledge-based communities, which in turn increases employee communication and collaboration. It is vital since through active communica-tion and collaborative efforts can employees build common basis for shared understandings that evolve into stronger relationships embedded with trust. To this aim, the electronic communication network allows the formation of social network to be more viable to rapid mobilization and assimilation of knowledge assets in the organizations.The purpose of this study is to investigate: (1) the impact of person-environment fit(person-job fit, person-per-son fit, person-group fit, person-organization fit) on social capital(network ties, trust, norm, shared language); (2) the impact of information systems acceptance factors(availability, perceived usefulness, perceived ease of use) on social capital; (3) the impact of social capital on personal performance(work performance, work satisfaction); and (4) the mediating role of social capital between person-environment fit and personal performance. In general, social capital is defined as the aggregated actual or collective potential resources which lead to the possession of a durable network. The concept of social capital was originally developed by sociologists for their analysis in social context. Recently, it has become an increasingly popular jargon used in the manage-ment literature in describing organizational phenomena outside the realm of transaction costs. Since both environmental factors and information systems acceptance factors affect the network of employee's relation-ships, this study proposes that these two factors have significant influence on the social capital of employees. The person-environment fit basically refers to the alignment between characteristics of people and their envi-ronments, thereby resulting in positive outcomes for both individuals and organizations. In addition, the in-formation systems acceptance factors have rather direct influences on the social network of employees.Based on such theoretical framework, namely person-environment fit and social capital theory, we develop our research model and hypotheses. The results of data analysis, based on 458 employee cases are as follow: Firstly, both person-environment fit(person-job fit, person-person fit, person-group fit, person-organization fit) and information systems acceptance factors(availability·perceived usefulness, perceived ease of use) sig-nificantly influence social capital(network ties, norm, shared language). In addition, person-environment fit is a stronger factor influencing social capital than information systems acceptance factors. Secondly, social capital is a significant factor in both work satisfaction and work performance. Finally, social capital partly plays a mediating role between person-environment fit and personal performance.Our findings suggest that it is vital for firms to understand the importance of environmental factors affecting social capital of employees and accordingly identify the importance of information systems acceptance factors in building formal and informal relationships of employees. Firms also need to reflect their recognition of the importance of social capital’s mediating role in boosting personal performance. Some limitations arisen in the course of the research and suggestions for future research directions are also discussed.