We report an optimized chemical vapor transport method to grow single crystals of (Mn1−xNix)2P2S6 where x = 0, 0.3, 0.5, 0.7, and 1. Single crystals up to 4 mm × 3 mm × 200 μm were obtained by this method. As-grown crystals are characterized by means of scanning electron microscopy and powder X-ray diffraction measurements. The structural characterization shows that all crystals crystallize in monoclinic symmetry with the space group C2/m (No. 12). We have further investigated the magnetic properties of this series of single crystals. The magnetic measurements of the all as-grown single crystals show long-range antiferromagnetic order along all principal crystallographic axes. Overall, the Néel temperature TN is non-monotonous; with increasing Ni2+ doping, the temperature of the antiferromagnetic phase transition first decreases from 80 K for pristine Mn2P2S6 (x = 0) up to x = 0.5 and then increases again to 155 K for pure Ni2P2S6 (x = 1). The magnetic anisotropy switches from out-of-plane to in-plane as a function of composition in (Mn1−xNix)2P2S6 series. Transport studies under hydrostatic pressure on the parent compound Mn2P2S6 evidence an insulator-metal transition at an applied critical pressure of ~22 GPa.