β-Ga2O3 is a wide bandgap semiconductor that is attractive for various applications, including power electronics, transparent conductive electrodes, etc. Electrical and optical properties of Ga2O3 are affected by the presence of dopants/contaminants and/or intrinsic defects. Here, we investigate the electrical and optical properties of transition metals like Co and Cr since they are often unintentionally present during the growth or used as intentional dopants. This is done by using magnetic resonance spectroscopy and magneto-optical characterization techniques. We determine spin- Hamiltonian parameters of the Cr3+ ground-state and first excited-state as well as the spin-Hamiltonian parameters of Co2+.