Evolved gas analysis (EGA), infrared attenuated reflection (ATR), and Raman spectroscopy experiments are used to study hydrogen evolution in hydrogenated microcrystalline silicon carbide (μc-Si1−xCx:H) films prepared by plasma-enhanced chemical vapor deposition. The results are compared with microcrystalline silicon (μc-Si:H). The effused hydrogen and carbon-hydride groups (CH, CH2, and CH3) are measured up to 800 °C. Their EGA curves have a peak at 410 °C, attributed to the methyl groups incorporated in the amorphous matrix during the deposition process. Moreover, hydrogen evolution curves show narrow and sharp peaks centered at 425 and 520 °C, corresponding to hydrogen desorbing from silicon hydrides at grain boundaries. While its content is more important than hydrogen bonded to silicon in the amorphous and denser crystalline regions of μc-Si1−xCx:H, but remains lower than in the μc-Si:H film. Raman and ATR data indicate that the μc-Si1−xCx:H film is composed of small size silicon crystallites embedded in a hydrogenated amorphous silicon carbide matrix and confirmed that carbon is incorporated in the amorphous matrix as methyl groups (CH3), inducing a decrease in SiHx groups compared to the μc-Si:H film.