Conversion of carbon dioxide into value-added chemicals through sunlight is a promising approach to reducing our reliance on fossil fuels. Spin provides another freedom to manipulate the photocatalytic CO2 reduction (CO2RR) process and enhance the corresponding properties of optoelectronic applications. In this work, improved photocatalytic CO2RR efficiency was obtained by manipulating spin-polarized species in inorganic halide perovskite microcrystals (MCs) with the introduction of manganese cations (Mn2+) and an employment of a magnetic field. Mn2+-doped CsPbBr3 MCs were prepared through self-assembly process, where Mn2+ is incorporated into CsPbBr3 matrices successfully. Introducing Mn2+ into CsPbBr3 matrices not only induces structural change but also generates new emission band as well as magnetic properties. Thereby, Mn2+-doped CsPbBr3 MCs show significantly enhanced photocatalytic CO2RR properties in contrast with pristine samples (the CO yield is significantly elevated from 22.1 to 41.9 μmol/g in Mn2+-doped CsPbBr3 MCs), as they generate spin-polarized electrons with the introduction of Mn2+. Remarkably, the photocatalytic CO2RR of Mn2+-doped CsPbBr3 MCs is greatly improved under the employment of a magnetic field, achieving 5.0 times higher performance compared to pristine CsPbBr3 MCs when the magnetic field strength is 300 mT. This enhancement is experimentally demonstrated by using magnetic circular dichroism spectroscopy. The increased photocatalytic CO2RR efficiency of Mn2+-doped CsPbBr3 MCs stems from the cooperative doping of Mn2+ and the application of magnetic fields, which generates more spin-polarized photoexcited carriers, thereby leading to extended carrier lifetime and reduced recombination process. These findings demonstrate that introducing spin into optoelectronic semiconductors is a powerful approach to enhancing photocatalytic CO2RR efficiency.