The stoichiometric intermetallic compound NbSi2 has been synthesized by mechanical alloying (MA) elemental Nb and Si powders. The alloying process has been investigated by means of x-ray diffraction (XRD) and differential scanning calorimetry (DSC). It was found that the formation of the Nb2Si intermetallic compound occurs abruptly after 65 min of milling without any interruptions during the alloying process. However, short interruptions at a 5 min interval during ball milling result in a gradual reaction for the formation of the NbSi2 compound as well as a new metastable bcc structured solid solution. We conclude that the temperature rise during mechanical alloying plays an important role in initiating the abrupt reaction after an incubation milling time.