The electrical resistivity and the Hall coefficient of thin polycrystalline MoSi2films were measured as a function of temperature from 4.2 to 300 K. The transverse and longitudinal magnetoresistances have been determined at temperatures between 2 and 50 K at fields up to 10 T. Samples of both the high‐temperature tetragonal MoSi2phase and the low‐temperature hexagonal phase have been prepared. The Hall coefficient of tetragonal MoSi2changes sign with temperature, which means that this compound is a multiband conductor, and thus no reliable value for the carrier concentration can be derived from Hall measurements alone. Magnetoresistance data have therefore been analyzed with a simple two‐band model in order to determine the dominant carrier type in both MoSi2structures. In tetragonal MoSi2, electrons and holes are present in equal concentrations, whereas in hexagonal MoSi2holes are the dominating type of carrier.