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Converting ambient vibration energy into electrical energy by using piezoelectric energy harvester has attracted a lot of interest in the past few years. In this paper, a topology optimization based method is applied to simultaneously determine the optimal layout of the piezoelectric energy harvesting devices and the optimal position of the mass loading. The objective function is to maximize the energy harvesting performance over a range of vibration frequencies. Pseudo excitation method (PEM) is adopted to analyze structural stationary random responses, and sensitivity analysis is then performed by using the adjoint method. Numerical examples are presented to demonstrate the validity of the proposed approach.