The observation of insulators to metallic conduction leads to vigorous study in transition metal-doped GdMnO3. Present study reveals the detailed study of structural correlation to electrical properties of transition metal element doped polycrystalline GdMn1-xTxO3 (where T = Cr, Fe; x = 0, 0.10) solid solution. The structural properties and phase purity of the synthesized samples have been analyzed by XRD. The Rietveld refinement of XRD patterns shows that the samples are crystallized in orthorhombic symmetry having the Pnma space group. However, the doping of Cr and Fe affects the octahedral distortion and structural parameters. The Mn–O octahedral distortion in Cr and Fe doped GdMn1-xTxO3 is reduced compared to pure GdMnO3, which is confirmed by the Raman spectroscopy. The X-ray photoelectron spectroscopy study is further observed to study the multiple valence state of Cr, Fe, and Mn in the material, which affects the structural and electrical properties of doped GdMn1-xTxO3. The low-temperature complex dielectric, complex Impedance, and ac conductivity study reveal the anomalous change in the dielectric behavior of Cr and Fe doped GdMn1-xTxO3 compared to pure GdMnO3. Dielectric constant and impedance show a relatively high value in GdMnO3, but the values decrease after Cr and Fe doping. A rapid change with decreased dielectric constant values in GdMn0.9Cr0.1O3 is observed compared to GdMn0.9Fe0.1O3 and GdMnO3 in the temperature range of 300 K–80 K. The ac conductivity and activation energy study of polycrystalline GdMn1-xTxO3 reveal the transformation from insulator to semiconducting nature of the material.