By using deep level transient spectroscopy (DLTS) and light beam induced current (LBIC) the behavior of chromium atoms in float‐zone n‐Si in the presence of dislocations and as‐grown vacancy complexes has been investigated. It was found that reactions of interstitial chromium atoms with dislocations and with as‐grown nitrogen–vacancy complexes reduce significantly the nucleation barrier for the formation of chromium‐silicide precipitates so that nearly all Cr atoms are collected into the precipitates even in quenched samples. These nano‐precipitates are very active in electron‐hole recombination and give a very broad DLTS signal related to deep donor electronic states in the bandgap of silicon.