Concentration photovoltaic (CPV) cells can only partially convert solar energy into electricity. The remaining energy is converted into thermal energy. This not only causes the temperature of the photovoltaic cell to rise, but also reduces the generation efficiency of the cell. The excess CPV heat can be recovered using a thermoelectric generator (TEG). The design of the structure of the TEG is important for a CPV-TEG hybrid system because it affects the heat dissipation of the CPV and thus its efficiency. In this study, a mathematical model of a hybrid system was established. The focus was to examine the effect of the structural parameters of the TEG on the system efficiency. The results showed that an optimal structural parameter (the ratio of the cross-sectional ratio to the height) with the value of 0.36 mm−1 existed for the TEG, enabling the system efficiency to reach a maximum of 41.73% under simulated conditions. In addition, the relationship between the optimal structural parameter, CPV temperature coefficient, concentration ratio, and cooling heat transfer coefficient was analyzed. The results can provide guidance for the efficient design of a hybrid system.