The influence of a third metallic component, vanadium, on the crystallization of quasi‐binary FeNiSiB metallic glasses is examined for three specimens with different vanadium contents. It is noticed that by adding a small amount of V (1 to 2 at%) to the amorphous matrix of FeNiSiB glasses the formation of α‐Fe structure‐like crystals is suppressed considerably and the precipitation of (FeNiV)3(SiB) and (FeNiV)2(SiB) intermetallic compounds is promoted. The V atoms, existing in the amorphous matrix of the samples, may play a role in impeding kinetically the clustering of metal atoms prior to the crystallization of FeNiSiB glasses and hence make the amorphous phase of these glasses more homogeneous in both, composition and structure.