Piezoelectric cantilever beams are commonly utilized to harvest energy from environmental vibrations due to their simple structures. This paper optimizes a single crystal trapezoidal hollow structure piezoelectric cantilever beam vibration energy harvester with a copper substrate to achieve high energy density at a low frequency. Finite element analysis (FEA) is adopted to optimize the size of the copper substrate at first, and the piezoelectric energy harvester (PEH) is further optimized with a trapezoidal hollow structure under the optimal size of the copper substrate. The developed PEH with a trapezoidal hollow structure (La = 20 mm, Lb = 15 mm, and Lh = 40 mm), with a copper substrate of 80 mm × 33 mm × 0.2 mm, can obtain the best output performance. Under the condition of 1 g acceleration, the resonance frequency and peak voltage output were 23.29 Hz and 40.4 V, respectively. Compared with the unhollowed PEH, the developed trapezoidal hollow structure PEH can reduce its resonant frequency by 12.18% and increase output voltage by 34.67%, while also supplying a power density of 7.24 mW/cm3. This study verified the feasibility of the optimized design through simulation and experimental comparison.