Among all antiferromagnetic transition metal monoxides, NiO presents the highest Néel temperature (TN ∼ 525 K). In this work, the size-dependent reduction of TN in NiO nanoparticles with average diameters (D) ranging from 4 to 9 nm is investigated by neutron diffraction. The scaling law followed by TN(D) is in agreement with the Binder theory of critical phenomena in low-dimensional systems. X-ray absorption fine structure measurements link the decrease of TN to the occurrence of size effects (average undercoordination, bond relaxation and static disorder) in the nearest and next-nearest Ni coordination shells that hold the key for the maintenance of the antiferromagnetic order.