Worldwide chemical industries are concerned towards pollution‐free and green processes. In this regard, alternative energy resource having minimal pollutant and toxins emission would be preferred. Jatropha curcas (JCO) is one of the important and alternative feedstock for biodiesel production. In the present work, JCO with higher (5.5%) free fatty acid (FFA) was used for transesterification using K–Mg composite catalyst. It found that 1:2 ratio of K/Mg was the best combination for efficient conversion of JCO to corresponding methyl esters. Physico‐chemical characterization of this novel catalyst exhibited improved surface area with adequate porosity as well as basicity helping its exceptional catalytic activity. Under optimum condition, 99.5% conversion was achieved using 10:1 ratio of methanol to JCO for 3 h at 70°C using 6 wt% of catalyst. This catalyst was truly heterogeneous in nature and almost retained its activity for subsequent re‐using for next five batches. The developed catalyst is highly efficient and greener in terms of lesser leaching behaviour and retaining the basic catalytic sites in the course of transesterification. The fuel properties of the biodiesel are fully complied with ASTM protocols; thus, research findings are significant to fulfil the demand of biodiesel in present scenario.