The charge stability of electret materials can directly affect the performance of electret-based devices such as electrostatic energy harvesters. In this paper, a spray-coating method is developed to deposit an electret layer with enhanced charge stability. The long-term stability of a spray-coated electret is investigated for 500 days and shows more stable performance than a spin-coated layer. A second-order linear model that includes both the surface charge and space charge is proposed to analyze the charge decay process of electrets in harsh environments at a high temperature (120 °C) and high humidity (99% RH); this model provides better accuracy than the traditional deep-trap model. To further verify the stability of the spray-coated electret, an electrostatic energy harvester is designed and fabricated with MEMS (micro-electromechanical systems) technology. The electret material can work as both the bonding interface and electret layer during fabrication. A maximum output power of 11.72 μW is harvested from a vibrating source at an acceleration of 28.5 m/s. When the energy harvester with the spray-coated electret is exposed to a harsh environment (100 °C and 98% RH), an adequate amount of power can still be harvested even after 34 h and 48 h, respectively.