Nd_0.95MnO_3±δ synthesized by solid state route crystallizes into (O′-type) orthorhombic phase. The O′-type orthorhombic structure shows distortion of MnO₆ octahedra due to orbital characteristic of Jahn–Teller effect of Mn³⁺ cations. Above ~1012 K these MnO⁶ octahedra become nearly regular. There is no change in symmetry however structural phase transition from O′-type to O-type orthorhombic structure is observed. Electrical conductivity studies further elucidate the observed structural phase transition.