The orthochromites La_0.7RE_0.1Ca_0.2CrO₃ (RE = \(Nd\),\(Sm\), and \(Eu\)) were prepared by solid-state reaction and the structural, microstructural, optical, and magnetic properties were investigated. The XRD revealed an orthorhombic perovskite structure. The UV–visible revealed the bandgap energy values: 2.81, 2.98, and 3.12 eV for \(Nd\), \(Sm\), and \(Eu\) doped samples, respectively. It is explained by the creation of the localized state. The refractive index, Urbach energy, and optical conductivity were investigated. The magnetization investigation revealed that the Néel temperature decreases with decreasing substituting ionic radius. Below T_N, all samples exhibit weak ferromagnetic behavior due to the t-e hybridization caused by intrinsic distortions. The \(Nd\) and \(Sm\) doped samples show spin reorientation due to the exchange interaction between the Sm³⁺/Nd³⁺ and Cr³⁺. The negative magnetization of the \(Nd\)-doped sample indicates its possible use as a volatile memory device. Regarding the \({E}_{g}\) values, our samples could be suitable candidates for optoelectronic devices.