This study presents multistability mechanisms that can enhance the energy harvesting performance of a piezoelectric energy harvester (PEH) with geometrical nonlinearities. To configure triple potential wells, static bifurcation diagrams in the structural parameter plane are depicted. On this basis, the key structural parameter is considered, of which three reasonable values are then chosen for comparing and evaluating the performances of the triple-well PEH under them. Then, intra-well responses and the corresponding voltages of the system are investigated qualitatively. A preliminary analysis of the suitable energy-harvesting conditions is carried out, which is then validated by numerical simulations of the evolution of coexisting attractors and their basins of attraction with variations in the excitation level and frequency. It follows that, under a low-level ambient excitation, the intra-well responses around the trivial equilibrium dominate the energy-harvesting performance. When the level of the environmental excitation is very low, which one of the three values of the key structural parameter is the best for improving the performance of the PEH system depends on the range of the excitation frequency; when the excitation level increases sufficiently to induce inter-well responses, the maximum one is the best for improving the performance of the PEH. The findings provide valuable insights for researchers working in the structure optimization and practical applications of geometrically nonlinear PEHs.