Through the analysis of the risk transmission mechanism of chemical substances in toys, this paper identifies risk sources, transmission carriers, key nodes, and risk recipients, and draws a risk transmission path diagram. Taking the risk factors in the supply chain system as the research subject, this paper constructs a risk index system for chemical substances’ limit in toys, and calculates the probability of risk and the degree of influence by the fuzzy evaluation method. Based on the Bayesian network model, this paper analyzes the causality of risk transmission effects. Through the comprehensive use of fuzzy evaluation and Bayesian network methods, a relatively complete chemical substance risk transmission path assessment system has been established using China’s Guangdong toy companies as the data store to provide a feasible basis for responding to the risk control measures of toxic and hazardous chemical substances in toys.