The reverse water-gas shift (RWGS) reaction offers a sustainable pathway for converting CO2 into CO, thereby facilitating syngas production. A stable and efficient catalyst is essential for ensuring practical applications without the risk of deactivation. In this study, perovskite oxide supports FeMnO3 (FM), ZrCaO3 (ZC), LaFeO3 (LF), and LaCoO3 (LC) were synthesized via the scalable and facile Pechini sol-gel method and impregnated with 5 wt% Ni and 5 wt% Cu to regulate the redox activity, reducibility, and thermal stability. The comprehensive characterization, including ICP-SFMS, XRD, H2-TPR, TGA, N2 Physisorption, XPS, and SEM, were conducted, confirming successful supported metals addition, high perovskite crystallinity, surface NiO/CuO formation, lower reduction temperatures and enhanced thermal stability. Catalytic testing from 200 to 700°C with different CO2:H2 ratios and feed compositions revealed high RWGS performance at 700°C with 15 vol% CO2, and CO2:H2 = 1:4. Under these improved conditions, Ni- and Cu-impregnated LaCoO3 achieved approximately 66% CO2 conversion with 98–100% CO selectivity. The catalysts demonstrated almost stable performance over 70 h with CO2 conversion stabilizing at 59.2% and maintaining a high CO selectivity (97.5%), with Cu contributing to improved stability by mitigating Ni deactivation. The catalyst retained the structural stability which was revealed by post-reaction XRD and SEM showing high crystallinity and minimal morphological changes. The higher performance of the LC catalyst is attributed to preserved Co3 +/Co2+ redox chemistry, and Ni and Cu supported metals effects, resulting in enhanced CO2 activation and electron transfer. This work demonstrates a dual Ni-Cu impregnation approach on LaCoO3 that enhances stability and RWGS performance, establishing it as a durable catalyst for RWGS applications.