Herein we reported the crystal structure and crystal chemistry of orthorhombic perovskite type Nd₂CuTiO₆ in between 2 K and 290 K as observed from the in situ temperature-dependent powder neutron diffraction (PND) studies. It is observed that the cations in octahedral sites are statistically occupied, and the ambient temperature orthorhombic structure is retained throughout the temperature range of the study. Absence of any long-range magnetic ordering down to 2 K is confirmed by both low-temperature PND and magnetization studies. The lattice shows strong anisotropic thermal expansion with increasing temperature, viz. almost no or feeble negative expansion along the a-axis while appreciably larger expansion along the other two axes (α_b = 10.6 × 10⁻⁶ K⁻¹ and α_c = 9.8 × 10⁻⁶ K⁻¹). A systematic change in the rotation of octahedral units with temperature was observed in the studied  temperature range, while the expansion of unit cells is predominantly associated with the polyhedral units around the Nd³Ions. The temperature-dependent relative change in unit cell parameters as well as coefficients of axial thermal expansion show anomalous behavior at lower temperatures, and that seems to be related to the electronic contributions to lattice expansion.