Phase-pure CsSnI3, FASnI3, Cs(PbSn)I3, FA(PbSn)I3 perovskites (FA = formamidinium = HC(NH2)2 +) as well as the analogous so-called vacancy-ordered double perovskites Cs2SnI6 and FA2SnI6 are mechanochemically synthesized. The addition of SnF2 is found to be crucial for the synthesis of Cs-containing perovskites but unnecessary for hybrid ones. All compounds show an absorption onset in the near-infrared (NIR) region, which makes them especially relevant for photovoltaic applications. The addition of Pb(II) and SnF2 is crucial to improve the electronic properties in 3D Sn(II)-based perovskites, in particular their charge carriers mobility (≈0.2 cm2 Vs−1) which is enhanced upon reduction of the dark carrier conductivity. Stokes-shifted photoluminescence is observed on dry powders of Sn(II)-based perovskites, which makes these materials promising for light-emitting and sensing applications. Thermal stability of all compounds is examined, revealing no significant degradation up to at least 200 °C. This meets the requirements for standard operation conditions of most optoelectronic devices and is potentially compatible with thermal vacuum deposition of polycrystalline thin films.