In this research, the optimized experimental conditions to obtain CaO supported KCl (KCl/CaO) as an efficient heterogeneous basic catalyst to produce no‐glycerol biodiesel using tri‐component (canola oil, dimethyl carbonate [DMC], and methanol) coupling transesterification was established. The solid base catalyst was prepared by wet impregnation of CaO in KCl solution and calcination subsequently, which greatly improved the reaction efficiency with high biodiesel yield of 96.4% at only 2 h. The KCl/CaO was characterized by techniques, such as BET surface area, XRD, CO2‐TPD, and SEM. Then, it was observed that the KCl introduced not only differed from CaO particles in the surface area and number of basic sites but also changed its base strength significantly. To obtain an improvement in conversion of canola oil, the influence on the catalytic performance of several kinetic parameters, such as mass ratio of catalyst to oil, reaction time, and molar ratio of methanol/oil/DMC were evaluated separately.Novelty or Significance: In this work, it was found that the catalytic performance of CaO‐based catalyst to coupling transesterification for no‐glycerol biodiesel production can be greatly improved by modifying CaO with KCl. As a result, the time to obtain as high as 96.4% yield of biodiesel over KCl/CaO can be greatly shortened from 5 to 2 h compared with common CaO. © 2018 American Institute of Chemical Engineers Environ Prog, 38: 647–653, 2019