Abstract Ethyl propionate can be produced from CO, C 2 H 4 , and CH 3 CH 2 OH as raw materials by ethylene hydroesterification in one step. In this paper, a solvent‐free composite catalytic system (Ru/CeO 2 ‐NaI‐NaOH) is developed to catalyze the hydroesterification of C 2 H 4 , CO, and C 2 H 5 OH. The formation and inhibition mechanisms of 3‐pentanone and acetal are studied, and the pathway for the generation of ethyl propionate has also been analyzed. The factors that influence the performance of catalytic system were researched, such as catalyst reduction temperature, the addition of Ru/CeO 2 , reaction temperature, reaction time, the partial pressure of CO, and so forth. In Ru/CeO 2 ‐NaOH‐NaI heterogeneous catalytic system, at the experiment conditions of 3 MPa and 180 °C, the C 2 H 4 conversion and the ethyl propionate selectivity are 66.7% and 92.0%, respectively after 4 h reaction. This work presents a strategy for the production of propionate by ethylene hydroesterification, catalyzed by a heterogeneous catalytic system.