The nitrogen dissociation and plasma parameters during radio frequency sputtering of lithium phosphorus oxynitride thin films in nitrogen gas are investigated by mass appearance spectrometry, electrostatic probes and optical emission spectroscopy, and the results are correlated with electrochemical properties and microstructure of the films. Low pressure and moderate power are associated with lower plasma density, higher electron temperature, higher plasma potential and larger diffusion length for sputtered particles. This combination of parameters favors the presence of more atomic nitrogen, a fact that correlates with a higher ionic conductivity. Despite of lower plasma density the film grows faster at lower pressure where the higher plasma potential, translated into higher energy for impinging ions on the substrate, resulted in a compact and smooth film structure. Higher pressures showed much less nitrogen dissociation and lower ion energy with thinner films, less ionic conductivity and poor film structure with large roughness.