The structural, compositional and electronic properties of the a-Si:H/a-SiN//x:H interface are reported. High resolution TEM and light/dark ESR studies conclude that the interface has a finite width of the order of 10 Angstrom. In addition, there is a high density of charges residing near the interface. Band bendings occur in both a-Si:H and a-SiN//x:H, resulting in few neutral dangling bonds in the a-Si:H/a-SiN//x:H multilayer structure. The depletion width in the nitride is of the order of 100 Angstrom. The slow decay of the LESR in multilayers with thin sublayers is attributed to charges trapped in the slow states in the nitride.