Biochar (BC) recently gained attention as an additive for anaerobic digestion (AD). This work aims at a critical analysis of the effect of six BCs, with different physical and chemical properties, on the AD of mixed wastewater sludge at 37 °C, comparing their influence on methane production and AD kinetics. AD batch tests were performed at the laboratory scale operating 48 reactors (0.25 L working volume) for 28 days with the addition of 10 g L−1 of BC. Most reactors supplemented with BCs exhibited higher (up to 22%) methane yields than the control reactors (0.15 Nm3 kgVS−1). The modified Gompertz model provided maximum methane production rate values, and in all reactors the lag-phase was equal to zero days, indicating a good adaptation of the inoculum to the substrate. The potential correlations between BCs’ properties and AD performance were assessed using principal component analysis (PCA). The PCA results showed a reasonable correlation between methane production and the BCs’ O–C and H–C molar ratios, and volatile matter, and between biogas production and BCs’ pore volume, specific surface area, and fixed and total carbon. In conclusion, the physic-chemical properties of BC (specifically, hydrophobicity and morphology) showed a key role in improving the AD of mixed wastewater sludge.