β-Ga2O3 is a wide bandgap semiconductor that is attractive for various applications, including power electronics and transparent conductive electrodes. Its properties can be strongly affected by transition metal impurities commonly present during the growth such as Cr. In this Letter, we determine the electronic structure of Cr3+ by performing a correlative study of magneto-photoluminescence (magneto-PL) and electron paramagnetic resonance. We unambiguously prove that the so-called R1 and R2 PL lines at around 1.79 eV originate from an internal transition between the first excited state (2E) and the 4A2 ground state of Cr3+. The center is concluded to have monoclinic local symmetry and exhibits a large zero-field splitting (∼147 μeV) of the ground state, which can be directly measured from the fine structure of the R1 transition. Furthermore, g-values of the first excited state are accurately determined as ga = 1.7, gb = 1.5, and gc* = 2.1. Our results advance our understanding of the electronic structure of Cr in β-Ga2O3 and provide a spectroscopic signature of this common residual impurity.