We present a pair distribution function (PDF) analysis from neutron diffraction data of the Ni1−xVx alloy in the Ni-rich regime. Such structural study aims to clarify the origin of the magnetic inhomogeneities associated with the quantum Griffiths phase close to the ferromagneticparamagnetic quantum phase transition. The PDF analysis successfully reveals the details of the structure and chemical distribution of our Ni1−xVx polycrystalline samples prepared with hightemperature annealing and rapid cooling protocol. This study confirms the expectations that all Ni1−xVx samples with 0 ≤ x ≤ 0.15 crystallize in a single phase fcc structure with some residual strain. The increase of the lattice constant and the atomic displacement parameter with Vconcentration x is consistently explained by a random occupation of V and Ni-atoms on the lattice, with a radius ratio (rV/rNi) of 1.05. Probing alternate, simple models of the local PDF, such as V-clusters or ordered structures (Ni8V, Ni3V) give inferior results compared to a random occupation. This investigation strongly supports that the magnetic clusters in the binary alloy Ni1−xVx originate from Ni-rich regions created from random occupation rather than from chemical clusters. It reveals that Ni1−xVx is one of the rare examples of a solid solution in a wide concentration regime (up to x = 0.15) persisting down to low temperatures (T = 15 K).