Effects associated with the change in the local density of photonic states in a periodic structure based on alternating a-Si1−xCx:H and a-SiO2 amorphous layers forming a one-dimensional (1D) photonic crystal have been analyzed. The use of a-Si1−xCx:H as the emitting material made it possible to examine the transformation of the photoluminescence spectrum contour that is comparable in width with the photonic stop-band. It was experimentally demonstrated that the emission is enhanced and suppressed in the vicinity of the stop-band. The relative intensities of the luminescence peaks at different edges of the stop-band vary with the detuning of the stop-band position and photoluminescence peak of a single a-Si1−xCx:H film. The Purcell effect in the system under consideration was theoretically described by the method in which the local density of photonic states is calculated in terms of a 1D model. It was shown that the specific part of local density of states substantially increases at the long-wavelength (low-frequency) edge of the stop-band of a 1D photonic crystal as a result of the predominant localization of the electric field of the light wave in the spatial regions of a-Si1−xCx:H which have a higher relative permittivity as compared with a-SiO2.