This study focuses on the application of a thermoelectric generator (TEG) tailored explicitly for the purpose of waste heat recovery from industrial kilns. To address this, the study proposes the integration of a TEG, a semiconductor device that effectively converts thermal energy into electrical energy, utilizing the Seebeck effect. Three multi-TEG system configurations were designed and modelled and their performance in recovering the waste heat was simulated using MATLAB Simulink. These configurations encompassed the series arrangement, the parallel arrangement, and the hybrid (series–parallel) arrangement. The outcomes of the simulations conclude the series arrangement as the most effective configuration for the multi-TEG system, showcasing a superior power output of 255 W and an efficiency of 52.26%.