Biochar, included as a soil amendment by EU Regulation 2019/1009, has been shown to increase soil organic C stock and nutrient retention. We investigated the effect of biochar incorporation alone (B) and in association with mineral (BMin), digestate (BDig) and slurry (BSlu) fertilization, compared to the respective controls without biochar (C, Min, Dig and Slu), in a silage maize–Italian ryegrass rotation, on yield, soil fertility parameters and nitrous oxide (N2O) emissions. Two types of biochar in three doses (0.2, 0.45, 0.9%) were tested in two cropping seasons. Biochar did not significantly affect maize yield; however, BDig tended to increase silage yield and the ear component compared to Dig, while BMin tended to reduce maize N uptake compared to Min. Biochar incorporation significantly increased soil organic C (+31%) and cation exchange capacity (CEC) (+13%) in all the fertilization treatments; BMin and BDig also showed an increase compared to biochar alone (B). Emission of N2O was mainly driven by fertilization, digestate exhibiting the highest emissions. Biochar addition decreased the cumulative N2O emissions consistently in all the fertilization treatments, though not significantly. The association of biochar with organic fertilizers, in particular digestate, appears promising in increasing the fertilizer efficiency and reducing N2O emissions.