Cu2SrSnS4 (CSTS) is a promising alternative candidate to Cu2ZnSnS4 (CZTS) for single- or multi-junction photovoltaics (PVs) owing to its efficient light-absorbing capability, earth-abundant, nontoxic constituents, and suitable defect properties. However, as a novel absorber material, several fundamental properties need to be characterized before further progress can be made in CSTS photovoltaics. In this letter, hybrid density functional theory (DFT) calculations have been used to comprehensively characterize for the first time, the electronic structure, band alignment, and optical properties of CSTS. It is demonstrated that CSTS possesses the ideal electronic structure (direct band gap of 1.98 eV and small photocarrier effective masses) and optical properties (high extinction coefficient and wide absorption) suitable for photovoltaic applications. Simulated X-ray photoelectron spectroscopy (XPS) valence band spectra using variable excitation energies show that Cu-3d electronic state dominates the valence band maximum of CSTS. Furthermore, the vacuum-aligned band diagram between CSTS and other common absorbers (CZTS, CIGS, CdTe) and the common n-type partner materials (CdS, ZnO) was constructed, which indicate staggered type-II band alignment at the CSTS/CdS and CSTS/ZnO interfaces. Based on these results, interface band offset engineering and alternative device architectures are suggested to improve charge carrier separation and power conversion efficiencies of CSTS.