The electrical properties of β-SiC ceramics were found to be adjustable through appropriate AlN–Y2O3 codoping. Polycrystalline β-SiC specimens were obtained by hot pressing silicon carbide (SiC) powder mixtures containing AlN and Y2O3 as sintering additives in a nitrogen atmosphere. The electrical resistivity of the SiC specimens, which exhibited n-type character, increased with AlN doping and decreased with Y2O3 doping. The increase in resistivity is attributed to Al-derived acceptors trapping carriers excited from the N-derived donors. The results suggest that the electrical resistivity of the β-SiC ceramics may be varied in the 104–10−3 Ω·cm range by manipulating the compensation of the two impurity states. The photoluminescence (PL) spectrum of the specimens was found to evolve with the addition of dopants. The presence of N-donor and Al-acceptor states within the band gap of 3C–SiC could be identified by analyzing the PL data.