First aid is a key factor in preventing further deterioration in an accident, saving lives, or improving treatment in emergencies. However, the reasons behind the willingness to provide first aid are still unclear. Therefore, this study aimed to investigate the role of social problem-solving and prosocial behavior in the dimension of first aid willingness. Self-administered questionnaires were used to evaluate the dimensions of first aid willingness (first aid willingness for peers, first aid willingness for strangers, knowledge, and negative emotions), social problem solving (positive problem orientation, negative problem orientation, rational problem solving, avoidance style, and impulsivity/carelessness) and prosocial behavior. A total of 497 school-aged students between the ages of 12 and 15 years (201 boys and 296 girls) participated in this study. Our results showed that positive problem orientation (p < 0.05) and rational problem solving (p < 0.001) are significant factors in determining first aid willingness for both peers and strangers. On the other hand, avoidance style orientation (p < 0.05) has a negative influence on the willingness to provide first aid to peers and strangers. Negative problem orientation (p < 0.001) only predicted negative emotions related to emergencies. Furthermore, prosocial behavior (p < 0.001) was more strongly associated with first aid willingness than social problem solving. Our study suggested that improving social competence could be a key factor in increasing first aid provision in real time, which could save lives in emergencies.