Gallium iron oxide GaFeO3 and the substituted GaFeO3 with Cr and Mn, i.e., Ga(Fe0.95Me0.05)O3, and (Ga0.95Me0.05)FeO3; Me=Cr and Mn, have been synthesized and investigated by X-ray powder diffraction. The refined structural parameters of the considered samples using the Rietveld technique showed a considerable distortion in the polyhedron around different cations, which may have an effect on the piezoelectricity of the studied samples. There are also changes in the interatomic distances between different cations, which may have a direct influence on the ferromagnetic properties of the samples. Crystallite size and microstrain are anisotropic and the largest along the b axis, which may be responsible for the piezoelectricity. The correlations between all these changeable parameters will be discussed.