X-band electron paramagnetic resonance (EPR) investigations of single crystals of Cr 3þ -doped dimethylammonium aluminium sulphate hexahydrate (DMAAlS) and dimethylammonium gallium sulphate hexahydrate (DMAGaS) are presented from room temperature down to liquid helium temperature. Both crystals undergo an order-disorder phase transition to ferroelectric phase at T C1 ¼ 152 K and T C1 ¼ 134 K, respectively. Additionally, DMAGaS undergoes a first-order transition into a low temperature non-ferroelectric intermediate phase at T C2 ¼ 116 K and into a low temperature antiferroelectric phase at about T C3 ¼ 60 K. The spin Hamiltonian parameters have been determined for all observed in both crystal phases. Remarkable EPR line width changes with observed triplets confirm the order-disorder character of the ferroelectric phase transition and demonstrate freezing-out of dimethyl ammonium reorientations, which is a primary reason for this transition. The doubled number of EPR lines in comparison to the paraelectric and ferroelectric phases in DMAGaS indicates a unit cell doubling in antiferroelectrics phase below 60 K.