The motivational effect of pay for performance (PFP) on employees has been widely considered by academic and practical circles, and its influence on the subsequent psychology and behavior of employees is also increasingly rich. However, as a double-edged sword of organizational management, PFP has not been studied from the perspective of discrete emotions to explore its impact on employees’ innovative behavior and unethical behavior. Drawing on the cognitive appraisal theory of emotions, our work aims to uncover the effect of PFP on employees’ emotions and behaviors. Results from a multi-wave survey of 497 samples and a scenario experiment study revealed that PFP was correlated with both inspiration and anxiety, which in turn respectively associated with innovative behavior and unethical behavior; The positive indirect effect of PFP on innovative behavior through inspiration was stronger when employees had higher (vs. lower) extraversion, while the positive indirect effect of PFP on unethical behavior through anxiety was stronger when employees had higher (vs. lower) neuroticism. Therefore, this study has enriched the theoretical research of discrete emotion mechanisms and provided a theoretical basis and decision-making reference for the implementation of PFP practice in organizations.