Single crystals of two organic-inorganic hybrid (OIH) perovskites containing 1,5 pentylenediammonium, [NH3-(CH2)5–NH3] MnCl3.47Br0.53 (C5MnCB) and [NH3-(CH2)5–NH3] CoCl2.72Br1.28 (C5CoCB) were grown from solution by evaporation. The structure is investigated by single crystal x-ray diffraction, and infrared and Raman spectroscopy is used to help proper space group selection. The C5MnCB hybrid perovskite crystallizes in the orthorhombic space group Ima2, with unit cell parameters a = 23.9358(11) Å, b = 7.4110(3) Å, c = 7.1765(4) Å, V = 1273.03(11) Å3 and Z = 4. In this sample two types of disorder are found: a preferential substitution of Cl by Br, and a dynamical disorder caused by the rotation of the NH3+ group. The C5CoCB hybrid perovskite crystallizes in the monoclinic space group P21/c, with unit cell parameters a = 7.1914(14) Å, b = 16.265(4) Å, c = 11.248(2) Å, β = 98.033(7)°, V = 1302.7(5) ų and Z = 4. In this compound a random Cl–Br occupancy is present. Based on UV–Vis spectroscopy and thermal stability measurements, we suggest possible photovoltaic and visible light photocatalytic applications.