Thermoelectric application has been widely researched due to its various advantages. Its use has been limited to niche industrial applications and exploratory research development due to the poor economic viability. It is essential to achieve the optimum system performance to improve the economic viability. In view of that, this study aims to improve the system performance by adopting the phase change materials (PCM) and heat transfer enhancement to establish improved thermal conditions. It experimentally investigates the effects of PCM and heat transfer enhancement on the open-circuit voltage and electrical energy of thermoelectric generator (TEG) system. Results indicate that the phase change temperature, thickness and thermal conductivity of PCM have a considerable impact on the electrical energy generated by TEG. An increase in absorption coefficient by surface coating can lead to an increase in electrical energy. However, the total electrical energy under forced convection is not obviously increased comparing with the natural convection case. The results achieved in this study indicate that suitable PCM and heat transfer enhancement measures should be considered according to the working conditions of TEG.