The new generation of post-90s and post-00s employees is increasingly becoming the main body of innovation. They challenge authority, criticize tradition, and even break the norms or violate orders to carry out bootleg innovation behaviors. Based on conservation of resource theory, this study takes Chinese supervisor-subordinate Guanxi as a conditional resource. From the perspective of the function of the resource itself, this study explores the mechanism of Chinese supervisor-subordinate Guanxi through psychological security on the bootleg innovation behavior, and then discusses the moderating effect of critical thinking on the influence mechanism from the perspective of the utilization of resources. The empirical study of 301 questionnaires shows that supervisor-subordinate Guanxi can positively influence the bootleg innovation behavior of employees, and this influence is generated through the psychological security of employees, that is, psychological security plays a mediating role between them. Critical thinking as an individual characteristic moderates the mediating effect. This study further suggests that superiors should take the initiative to break down power barriers, maintain and develop relationships with subordinates, and foster a sense of psychological security in subordinates to encourage bootleg innovation behaviors.