Two new tin(II) phosphates, SnII SnIV (PO4 )2 and SrSn(PO4 )PO2 (OH)2 , were synthesized by the high-temperature solution method and hydrothermal method, respectively. Theoretical study indicates that by introducing tin(II) with stereochemical activity lone pairs (SCALP) in metal phosphates, the birefringence was enhanced, 0.048@1064 nm for SnII SnIV (PO4 )2 and 0.080@1064 nm for SrSn(PO4 )PO2 (OH)2 .