The formation of nanoscale vanadium carbide (VC) precipitates is reported in steels subjected to two different thermal treatments. The thermal treatments lead to either interphase precipitation (IP) or random precipitation (RP). Small-angle neutron scattering measurements coupled with transmission electron microscopy analysis are performed to determine the VC precipitate volume fraction and size distribution. It is seen that the samples exhibiting IP show a higher number density of VC precipitates compared to those undergoing RP. Moreover, a broader size distribution of the precipitate radii is observed in the samples with RP, where lens-shaped nanoscale VC precipitates are found predominantly at grain boundaries (GBs) and sub-grain boundaries (SGBs), with smaller precipitates dispersed within the matrix. It is seen that the addition of carbon and vanadium does not increase the VC precipitate number density when the mechanism of precipitation is IP, whereas an increase in the VC precipitate number density with carbon and vanadium addition is seen in case of RP.