This is the first study on the ionothermal synthesis, intrinsic photoluminescence (PL), and dopant effects for tin(II) phosphite, a stereochemically active 5s(2) lone-pair-electron-containing compound, the fundamental properties of which have rarely been explored before. In a new deep-eutectic solvent, single-phased products of SnHPO3 (1) and Sn1-xMnxHPO3 (2) have been achieved in high yield. The crystalline powder of 1 is non-enantiomorphic, with an intense second-harmonic generation comparable to that of potassium dihydrogen phosphate. Under UV excitation, it unexpectedly emits white PL, an important intrinsic property never discovered in tin(II) oxysalts. Electron paramagnetic resonance hyperfine splitting characteristic of manganese has been detected on 2 and a three-pulse electron-spin-echo envelope modulation technique implemented to locate its corresponding location in the inorganic host. On the basis of temperature-dependent PL and lifetime measurements, the incorporated Mn2+ uncommonly acts as a sensitizer in enhancing white emission until extremely low temperatures, in which it would resume its normal role as an activator to give out characteristic orange light.