The research aims to examine the extent to which the perceived organizational support (POS) predicted career related self and environmental exploration via the mediation effect of career adaptability. Multi-group comparisons based on the gender, majors and places of origin were also performed to evaluate the differences among these variables. An internet survey was conducted to collect empirical data from 611 Chinese undergraduates. Structural equation modeling (SEM) was conducted to demonstrate the proposed relations in the model and multiple group analysis. Clearly supported was the direct relations between POS and career related self and environmental exploration and the mediation effect of career adaptability. The results also showed that gender and major are the moderating variables for the proposed model, and no significance difference among the rural and urban subgroups was found. POS could be effectively delivered to students in general, marginalized social groups, such as females and those majored in the humanities and social sciences in particular. Four dimensions of career adaptability (concern, control, curiosity and confidence) could also be targeted at in order to promote students’ sustainable employment. The findings provide a better understanding of the career construction model by incorporating the contextual factor in a collective cultural environment.