The structural, magnetic, and electronic properties of NdFe0.5Mn0.5O3 have been studied in detail using bulk magnetization, neutron/x-ray diffraction and first principles density functional theory calculations. The material crystallizes in the orthorhombic P bnm structure, where both Mn and Fe occupy the same crystallographic site (4b). Mn/Fe sublattice of the compound orders in to a G-type antiferromagnetic phase close to 250 K where the magnetic structure belongs to Γ1 irreducible representation with spins aligned along the crystallographic b direction. This is unconventional in the sense that most of the orthoferrites and orthochromites order in the Γ4 representation below the Néel temperature.This magnetic structure then undergoes a complete spin reorientation transition with temperature in the range 75 K > ∼ T > ∼ 25 K where the magnetic structure exists as a sum of two irreducible representations (Γ1+Γ2) as seen from neutron diffraction measurements. At 6 K, the magnetic structure belongs entirely to Γ2 representation with spins aligned antiferromagnetically along the crystallographic c direction having a small ferromagnetic component (Fx). The unusual spin reorientation and correlation between magnetic ground state and electronic structure have been investigated using first principles calculations within GGA+U and GGA+U+SO formalisms.