Single-layered and multi-layered 20–60 nm thick silicon nitride (Si3N4) dielectric nanofilms were fabricated using a low-pressure chemical vapour deposition (LPCVD) method. The X-ray photoelectron spectroscopy (XPS) confirmed less oxygen content in the multi-layered nanofilms. The capacitors with Si3N4 multilayer demonstrated a tendency to a higher breakdown voltage compared to the capacitors with Si3N4 single layer. Si3N4 nanofilms and capacitors with Si3N4 dielectric were exposed to 1 kGy dose of gamma photons. Fourier transform infrared (FTIR) spectroscopy analysis showed that no modifications of the chemical bonds of Si3N4 were present after irradiation. Also, gamma irradiation did not influence the breakdown voltage of the capacitors but decreased their capacitance measured at 1 MHz frequency. However, the multi-layered capacitors were not affected by radiation more than the single-layered capacitors. These findings suggest a promising process to fabricate nano-scaled multi-layered Si3N4 capacitors with improved breakdown voltage characteristics and resistance to ionizing radiation.