[en] Highlights: • Bi_0.3Pr_0.3Ca_0.4Mn_1-xCr_xO₃ (x = 0–0.14) samples were prepared by solid state method. • Substitution of Cr³⁺ at x = 0.08 destabilized CO state and induced ferromagnetic metallic phase. • Substitution of Cr³⁺ at x = 0.04 produced large magnetoresistance effect. • Possible conduction mechanisms involved are well described by scattering and hopping processes. - Abstract: The effect of Cr³⁺ substitution at Mn-site on the structure, magnetic and electrical properties of Bi_0.3Pr_0.3Ca_0.4Mn_1-xCr_xO₃ manganites were studied by using X-ray diffraction method, AC susceptibility and electrical transport measurements. All the samples with starting composition of Bi_0.3Pr_0.3Ca_0.4Mn_1-xCr_xO₃ (x = 0, 0.04, 0.08, 0.1, 0.12 and 0.14) were prepared using solid state method. R versus T curve shows that x = 0 sample exhibits a strong insulating behavior while Cr³⁺substitution at x = 0.08 induced metal-insulator (MI) transition at MI transition temperature (T_MI) of 56 K. The substitution for x = 0.08 successfully weakened the hybridization effect which may related to strong ferromagnetic (FM) interaction between Cr³⁺OMn³⁺ as well as Mn³⁺OMn⁴⁺. Further substitution of Cr³⁺ for x = 0.1 increased the T_MI to 58 K but decreased to 36 K for x = 0.12. Rietveld Refinement of the X-ray diffraction data showed a decreased of unit cell volume which indicated partial substitution of Cr³⁺ (0.615 Å) at Mn⁺³(0.64 Å) site. Susceptibility, χ′ versus temperature, T measurements, showed an increase of ferromagnetic-paramagnetic, FM-PM transition temperature, T_C from 66 K (x = 0.04) to 125 K (x = 0.14) which suggested that Cr³⁺ substitution enhanced the growth of FM phase. Fitting of the experimental data in the metallic region to scattering models suggested scattering involving a combination of electron-electron, electron-magnon, Kondo-like spin-dependent scattering, and electron-phonon interaction are responsible for the observed resistivity behavior. On the other hand, fitting in the insulating region suggests that resistivity behavior obeys the variable range hopping (VRH) model below the charge ordered temperature, T_CO for (x = 0) and T_MI T $T_{{\theta }_{D/2}}$ for x = 0.04–0.14 while at high temperatures involved small polaron hopping, SPH mechanism. Therefore, the enhanced double exchange mechanism (DE) indicates the substitution of Cr³⁺ increased the delocalization of charge carrier and destabilization of the CO-AFM state. It is suggested that such an increased of DE mechanism was related to the reduction of blocking mechanism which generated by the hybridization effect due to Bi 6s² lone pair.