Among other reliability concerns, the dielectric charging is considered the major failure mechanism which hinders the commercialization of electrostatic capacitive radio frequency micro-electro-mechanical systems (RF MEMS) switches. In this study, Kelvin probe force microscopy (KPFM) surface potential measurements have been employed to study this phenomenon. Several novel KPFM-based characterization methods have been proposed to investigate the charging in bare dielectric films, metal–insulator–metal (MIM) capacitors, and MEMS switches, and the results from these methods have been correlated. The used dielectric material is plasma-enhanced chemical vapor deposition (PECVD) silicon nitride. The SiNx films have been charged by using a biased atomic force microscope (AFM) tip or by electrically stressing MIM capacitors and MEMS switches. The influence of several parameters on the dielectric charging has been studied: dielectric film thickness, deposition conditions, and under layers. Fourier transform infra-red (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) material characterization techniques have been used to determine the chemical bonds and compositions, respectively, of the SiNx films. The data from the physical material characterization have been correlated to the KPFM results. The study provides an accurate understanding of the charging/discharging processes in dielectric films implemented in electrostatic MEMS devices.