Cooperation is essential for survival and should not be ignored. When making decisions whether to cooperate or not, people usually face conflict between maximizing personal interests at a social cost and maximizing collective interests at a personal cost. Within such context of social dilemmas, numerous studies have explored factors that facilitate cooperative behavior, and found that procedural fairness is the key antecedent to cooperation. However, the underlying mechanism of the procedural fairness – cooperative behavior link remains elusive. Moreover, past research mainly explored such link in same-sex person interaction scenarios, leaving an open question whether its link is consistent across gender. The current work aims to address these issues by exploring how procedural fairness affects cooperative behavior in opposite-sex person interaction scenarios, assessing the mediating role of cooperative expectations and the moderating role of others’ prior cooperative rates in this causal relation. A total of 152 undergraduates participated this experiment. The opposite-sex person interaction scenarios were generated by introducing participants with an opposite-sex stranger and telling participants to play series games with the stranger. Procedural fairness was manipulated in an allocation task, in which determining an allocation by chance was relatively fairer than by person willingness. Cooperation was subsequently studied by using the chicken game paradigm. Specifically, others’ prior cooperative rates were explicitly manipulated by informing participants the possibility that their interactive partner cooperated in previous experiments. In high cooperative rates condition, participants were informed that allocators who had participated this experiment before averagely chose to cooperate with 75% probability, whereas those in low cooperative rates condition were informed that previous allocators averagely chose cooperate with 25% probability. Next, cooperative behavior was measured by calculating the number of cooperation options in the six rounds; afterwards, cooperative expectations were measured by asking participants to assess how many rounds their partner would choose cooperation/aggression. Results showed that experiencing fair procedures facilitated subsequent cooperation with the opponent, and that the effects were mediated by enhanced expectations of cooperation. Moreover, the positive prediction of procedural fairness on cooperative behavior was stronger in low cooperative rates condition than in high cooperative rates condition. Additionally, the mediating role of cooperative expectations in the associations between procedural fairness and cooperative behavior was significant both in high and low cooperative rates condition, and such mediating effect of others’ prior cooperative rates was larger in low (vs. high) cooperative rates condition. The present work revealed that the effect of procedural fairness on cooperative behavior is robust, because such effect in same-sex person interaction scenarios could also be found in opposite-sex person interaction scenarios. Most importantly, the present work demonstrated that people use their experience of procedural fairness as a cue to formulate cooperative expectations of others and that they subsequently use these expectations to decide on their own cooperation, which would be moderated by interaction partners’ prior cooperative information. In sum, the present work not only shed light on understanding the relationship between procedural fairness and cooperative behavior, but also extended prior fair-related theories (e.g., Fairness Heuristic Theory) and Goal Expectation Theory.