Single crystals of Nd3+-doped Co-picromerite has been synthesized by the slow evaporation method. After two weeks on hold, the crystals obtained were characterized by different techniques, indeed X-ray powder diffraction (XRPD) shows that these compounds crystallize in the monoclinic system with space group P21/a. Complete dehydration of the double salt was obtained before reaching 200°C with a phase transition of KS around 570°C. The IR spectroscopic study confirms the vibrational modes of the sulfate groups and water molecules. Exciting at 473nm, the emission peaks associated with the 4F5/2→4I9/2, 4F3/2→4I9/2 and 4F3/2→4I11/2 transitions were observed. The luminescence decay curve was analyzed in the frame of the Inokuti-Hirayama model in order to obtain the intrinsic lifetime and the energy transfer parameter among Nd3+ions.