The presented study deals with the use of legumes intercropped with maize for the production of biogas from silage. The main goal was to find out whether silages made from mixed cultures can be used in biogas production and how the use of such silages affects qualitative and quantitative parameters of the fermentation process compared with the pure maize silage. Variants prepared were pure cultures of maize, bean, lupin, and white sweet clover. In addition, mixed cultures were prepared of maize and individual legumes. Measured values showed that in terms of dry matter (DM) yield, mixed culture silages are almost of the same or even better quality than silage made from the maize monosubstrate. Compared with the maize monoculture silage, the presence of white lupine, white sweet clover, and broad bean in silages statistically significantly increased the content of DM, ash, and acid detergent fiber (by more than 5%). Bean and lupine in mixed silages with maize significantly increased the content of lipids (on average by more than 1.2%). Legumes in silages were significantly decreasing contents of neutral detergent fiber, crude protein, and starch. Production of biogas from silages of maize monosubstrates and mixed substrates of maize with white lupin, maize with white sweet clover, and maize with broad bean was directly proportional to the content of CAR and starch in these substrates. A perspective variant was the mixed substrate of maize and sweet clover from which biogas production was only 6% lower than that from conventional maize silage. The highest yield was recorded in the maize monosubstrate (0.923 m3/kgVS). Variants of mixed substrates had a yield ranging from 0.804 to 0.840 m3/kgVS.