In emerging economies, the public sector offers a primary source of entrepreneurs. Yet existing studies of entrepreneurship mainly focus on how employees, in either private firms or academic institutions, develop entrepreneurial intentions, leaving the general public sector largely ignored. Given the fundamental differences between the public and private sectors, the current study undertakes a comparative analysis of sectoral differences in the formation of employees’ entrepreneurial intentions, along with a mediation assessment of entrepreneurial human and social capital. Findings from three archival data sources, at multiple levels, suggest that the two mediating mechanisms work in opposite directions: Public employment fosters entrepreneurial intentions through increased entrepreneurial human capital but inhibits entrepreneurial intentions through decreased entrepreneurial social capital. The mediating mechanisms also are differentially moderated by legal effectiveness and privatization.