Designing and discovering negative thermal expansion (NTE) materials is important in precisely controlled thermal expansion devices. In this work, the NTE of a cubic metal fluoride, ReO3-type VF3, was predicted by density functional theory within the quasi-harmonic approximation. These results reveal that cubic VF3 displays a negative thermal expansion behavior below 200 K, and the predicted minimum negative thermal expansion coefficient is approximately −6.4 × 10−6 K−1 at 80 K. The negative thermal expansion was mainly dominated by the prominently negative Grüneisen parameter situated at M(0.5,0.5,0) and R(0.5,0.5,0.5). The underlying mechanism was attributed to the anisotropic F atom vibration, where the amplitude of transverse vibration perpendicular to the V–F–V connection was much larger than that of the vibration along the parallel V–F–V direction. This research provides a good understanding of the relationship between NTE and crystal structure. [ABSTRACT FROM AUTHOR]