In order to improve the market activity and advocate the innovation of the whole people in China, some enterprises have made investment, but the effect is not high. In order not to lose competitiveness, the frequency of innovation behavior is very important. This study uses snowball sampling method to investigate employees of many companies in Xi'an. A total of 493 questionnaires were collected and the data were analyzed to study the impact of employees' psychological availability on employees' innovative behavior. The results of this study are as follows: (1) having verified the relationship between employees' psychological accessibility and employees' innovative behavior, between employees' psychological accessibility and error communication orientation, and between error communication orientation and employees' innovative behavior; (2) having verified the mediating role of error communication orientation between employees' psychological accessibility and employees' innovative behavior; (3) having verified the moderating role of enterprise knowledge sharing between employees' psychological accessibility and error communication orientation as well as between error communication orientation and employees' innovative behavior.