This study develops a hybrid photovoltaic-thermoelectric generator (PV-TEG) system to reduce dependence on fossil fuels and promote sustainable energy generation. However, the inherent randomness of real-world operational environments introduces challenges such as partial shading conditions and uneven temperature distribution within PV and TEG modules. These factors can significantly degrade system performance and reduce energy conversion efficiency. To tackle these challenges, this paper proposes an advanced optimal power extraction strategy and develops a chaotic RIME (c-RIME) optimizer to achieve dynamic maximum power point tracking (MPPT) across varying operational scenarios. Compared with existing methods, this approach enhances the effectiveness and robustness of MPPT, particularly under complex working conditions. Furthermore, the study incorporates a comprehensive assessment framework that integrates both technical performance and sustainability considerations. A broader range of realistic operational scenarios are analyzed, with case studies utilizing onsite data from Hong Kong and Ningxia for technical and environmental evaluations. Simulation results reveal that the c-RIME-based MPPT technique can effectively enhance system energy output with smaller power fluctuations than existing methods. For instance, under startup testing conditions, the c-RIME optimizer achieves energy output increase by up to 126.67% compared to the arithmetic optimization algorithm.