Abstract Single crystals of pure, Ca2+ and Sr2+ doped NH4Sb3F10 are grown by slow evaporation technique. The effect of dopants on the growth and physicochemical properties also have been investigated and reported for the first time. The grown crystals are characterized with the aid of single crystal X-ray diffractometry to confirm the crystal structure. EDAX studies are done to confirm the presence of dopants in the crystal lattice. The vibrational frequencies of various group ligands in the crystals have been derived from the Fourier transform infrared (FT-IR) spectrum. From the optical absorption spectrum the band gap energy was calculated and it was found to be 5.76, 6.29 and 6.35eV for pure, Ca2+ and Sr2+ doped NH4Sb3F10 crystals respectively. Thermal stability of the sample has been analysed using TG-DTA analysis. The activation energy of pure, Ca2+ and Sr2+ doped NH4Sb3F10 crystals were calculated from the dc conductivity measurements and it is found to be 0.2728, 0.2816 and 0.3622eV Experimental results shows improved physicochemical properties when the dopant is added to the pure material.