Life satisfaction reflects people’s life quality from subjective side. However, the existing researches mostly focus on the elderly, adolescents and those with physical or mental disorders, but few researches conducted on normal adults. Core self-evaluation is an advanced concept of personality, composed of four general concepts which are self-esteem, general self-efficacy, emotional stability and internal control. Many researches showed that core self-evaluation can effectively predicted people’s life satisfaction. However, few researches explored the mechanism how core self-evaluation predict people’s life satisfaction. Getting insight into people’s satisfaction of specific field in the life, we hypothesized core self-evaluation can not only directly affect life satisfaction, but also indirectly affect life satisfaction on the basis of the mediating effect of perceived social support, as from different sources, the perceived social support can have different effect. The purpose of this study was to explore the relationship between core self-evaluation and life satisfaction of employees, as well as test the mediating effects of perceived social support from different sources between the core self-evaluations and life satisfaction in different fields. There were 245 employees to participate in this study. CFA and structural equation modeling were used to test the theoretical model. The results indicated that: (1) core self-evaluation directly and positively predicted job satisfaction and self satisfaction; (2) family support fully mediated the relationship between the core self-evaluation and family satisfaction, and partially mediated core self-evaluation and self satisfaction; friend support fully mediated core self-evaluation and friend satisfaction. From the perspective of perceived social support from different sources, this study explored the mechanism how employees’ core self-evaluation predict their life satisfaction in different fields. It has shown that core self-evaluations directly affect non-relational life satisfaction, while indirectly affect relational life satisfaction on the basis of some kind of perceived social support’s mediating effect. It revealed that the different areas of life satisfaction shouldn’t be treated as the same. Greater influence of personality would work for non-relational life satisfaction, but the family harmony, being understood, and other support is significant for relational life satisfaction. The result of this study makes a contribution to further deepen the understanding of the mechanism of how the core self-evaluation effects on life satisfaction, and also can give some advices to increase life satisfaction and subjective well-being of employees.