Perovskite-type Nd(Cr 1-x Mn x )O 3 was stoichiometrically synthesized in the range 0 ≤ x ≤ 0.6 and has the orthorhombic GdFeO 3 -type structure with space group Pnma. The average (Cr, Mn)-O distance and the effective magnetic moment (μ eff ) indicate that the Mn 3+ ion is in a high-spin state with the (dε) 3 (dγ) 1 configuration. From the results of the electrical resistivity (ρ), Nd(Cr] 1-x Mn x )O 3 is a semiconductor and has a maximum ionization energy (ΔE) at x = 0.2. Rietveld analysis indicates that each (Cr, Mn)O 6 octahedron has little distortion and that the average angles for (Cr, Mn)-O(2)-(Cr, Mn) have a maximum value at x = 0.2, that is, the overlap between the cation d ε and oxygen pπ orbitals plays an important role in the electrical properties of Nd(Cr 1-x Mn x )O 3 .