Objective: The purpose of this study was to examine whether motivation for choosing a teaching profession and the perception of social support of newly-appointed childcare teachers would predict work adjustment, and to understand the mediating role of the perception of social support. Methods: The data was analyzed by using correlation, regression, and the verification of mediating effects. Results: First, there were significant correlations of active motivation and material motivation when choosing a teaching profession, perception of social support, and work adjustment. Second, active motivation and material motivation in relation to choosing a teaching profession, and the perception of social support, were the variables that could predict the work adjustment of newly-appointed teachers. Third, the social support perceived by newly-appointed teachers had partial-mediating effects on the relationship between active motivation in relation to choosing a teaching profession and work adjustment, as well as on the complete-mediating effects on the relationship between material motivation and work adjustment. Implications: The training institute should strengthen education that could foster active motivation of pre-service teachers, and daycare centers should establish a cooperative workplace culture for the psychological adjustment of newly-appointed teachers.