<p>A series of Ga_1-xAl_xFeO₃ (x = 0, 0.2, 0.4 and 0.6) solid solutions were synthesized through the conventional solid-state reaction method to investigate the effect of Al³⁺ substitution on their structural, microstructural, magnetic, and dielectric properties. Room temperature X-ray diffraction (XRD) and neutron diffraction (ND) analyses confirm the formation of the non-centrosymmetric <i>orthorhombic</i> structure across all compositions. Detailed Rietveld refinement of both XRD and ND patterns provided quantitative insights into lattice parameters, cation distribution, and structural distortions induced by Al³⁺ substitution. Raman spectroscopy further corroborates the formation of the <i>orthorhombic</i> phase, revealing 15 Raman-active vibrational modes characteristic of GaFeO₃. Scanning electron microscopy (SEM) micrographs exhibit well-defined grains and distinct grain boundaries, while progressive Al³⁺ substitution results in systematic grain size reduction. Low-temperature (5–300&#xa0;K) dc magnetization measurements, including zero-field-cooled (ZFC) and field-cooled (FC) protocols along with magnetic hysteresis (M-H) loops, reveal a clear paramagnetic-ferrimagnetic transition (<i>T</i>_N). Notably, <i>T</i>_N shifts toward higher temperatures with increasing Al³⁺ concentration, approaching room temperature. The enhancement in magnetic transition temperature is attributed to structural distortion and modified Fe–O–Fe superexchange interactions induced by Al³⁺ substitution. Temperature-dependent dielectric measurements exhibit anomalies near T_N, indicating significant indirect magnetoelectric coupling in all solid solutions. Overall, Al³⁺ substitution in GaFeO₃ effectively modulates magnetic ordering and enhances magnetodielectric coupling, highlighting the potential of Ga_1-xAl_xFeO₃ solid solutions for multifunctional and spintronic device applications.</p>