This paper presents the theoretical modeling and multiple-scale analysis of a novel piezoelectric energy harvester composed of a metal cantilever beam, piezoelectric films, and an axial preload spring at the moveable end. The harvester experiences mono- and bi-stable regimes as the stiffness of preload spring increases. The governing equations are derived with two high-order coupling terms induced by the axial motion. The literature shows that these high-order coupling terms lead to tedious calculations in the stability analysis of solutions. This work introduces an analytical strategy and the implementation of the multiple-scale method for the harvester in either the mono- or bi-stable status. Numerical simulations are performed to verify the analytical solutions. The influence of the electrical resistance, excitation level, and the spring pre-deformation on the voltage outputs and dynamics are investigated. The spring pre-deformation has a slight influence on the energy harvesting performance of the mono-stable system, but a large effect on that of the bi-stable system.