We explore the photovoltaic-relevant properties of the 2D MA2Pb(SCN)2I2 (where MA = CH3NH3(+)) perovskite using a combination of materials synthesis, characterization and density functional theory calculation, and determine electronic properties of MA2Pb(SCN)2I2 that are significantly different from those previously reported in literature. The layered perovskite with mixed-anions exhibits an indirect bandgap of ∼2.04 eV, with a slightly larger direct bandgap of ∼2.11 eV. The carriers (both electrons and holes) are also found to be confined within the 2D layers. Our results suggest that the 2D MA2Pb(SCN)2I2 perovskite may not be among the most promising absorbers for efficient single-junction solar cell applications; however, use as an absorber for the top cell of a tandem solar cell may still be a possibility if films are grown with the 2D layers aligned perpendicular to the substrates.