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Organic Rankine cycle (ORC) is an effective way to improve energy efficiency, and 2,3,3,3-tetrafluoropropene (R1234yf) is considered as a promising working fluid for ORC. However, the development of R1234yf in ORC is limited by its flammability, and the addition of 1,1,1,2-tetrafluoroethane (R134a) is an effective method to inhibit its flammability. In this paper, the combustion and interaction mechanism of R1234yf/R134a were investigated. Firstly, the combustion products of R1234yf/R134a were measured using an improved experimental device, the results showed a substantial reduction in the concentrations of CO, CO 2 , and HF with an increasing proportion of R134a. Then, the combustion mechanism of R1234yf/R134a was studied by ReaxFF-MD simulation. The initial decomposition time of R134a was found to be later than that of R1234yf, and a reduction in the production rate of combustion products was achieved with the addition of R134a. Furthermore, the combustion reaction was promoted by the increase in temperature. Finally, the main reaction pathways of working fluids were analyzed. The abstraction reaction of R134a with radicals and the scavenging of active radicals by flame retardant radicals were the key to inhibit the combustion reaction. The results have universal guiding significance for the safe application of R1234yf/R134a. • The combustion and interaction mechanism of R1234yf/R134a was investigated. • The combustion products of R1234yf/R134a with different proportions were measured. • The inhibitory effect of R134a on the combustion of R1234yf was studied. • The main reaction pathways of R1234yf/R134a were analyzed. [ABSTRACT FROM AUTHOR]