Recently bistable composite laminates have been investigated for broadband energy harvesting, by taking advantage of their nonlinear oscillations around the first vibration mode. However, it has been reported that the excitation acceleration needed for the desired large amplitude limit cycle oscillation is too high, if the first vibration mode is elevated to relative higher frequencies (60 Hz e.g.). This study investigates the feasibility of exploiting the nonlinear oscillations around the second vibration mode of a rectangular piezoelectric bistable laminate (RPBL), for broadband vibration energy harvesting at relative higher frequencies, but with relative low excitation acceleration. The proposed RPBL has three oscillation patterns around the second vibration mode, including single-well oscillation, chaotic intermittency oscillation and limit cycle oscillation. The broadband characteristics and the considerable energy conversion efficiency of the RPBL are demonstrated in experiments. The static nonlinearity and the dynamic responses of the RPBL are investigated by finite element method. Finite element analysis (FEA) reveals that the enhanced dynamic responses of the RPBL are due to its softening bending stiffness and the local snap through phenomenon. The FEA results coincide reasonably well with experimental results.