Angle-resolved secondary electron emission spectra were analyzed for studying the electron transmission properties of graphene when it is tightly bound to a metallic substrate and when it is decoupled from the latter. As respective model systems, graphene/Ni(111) and graphene/Au/Ni(111) were considered. We discovered two types of spectral structures linked with the transmission properties of graphene: bands related to scattering resonances and to umklapp reflection. These findings are interpreted based on an ab initio theory of the scattering of the outgoing electrons by the graphene overlayers. The experimental secondary electron emission maps are in good agreement with the calculations, indicating that such approach can be successfully applied for studying the electron transmission properties of a variety of two-dimensional materials.