The disclosure relates to a method of making molybdenum films utilizing boron and molybdenum nucleation layers. The resulting molybdenum films have low electrical resistivity, are substantially free of boron, and can be made at reduced temperatures compared to conventional chemical vapor deposition processes that do not use the boron or molybdenum nucleation layers. The molybdenum nucleation layer formed by this process can protect the substrate from the etching effect of MoCl5 or MoOCl4, facilitates nucleation of subsequent CVD Mo growth on top of the molybdenum nucleation layer, and enables Mo CVD deposition at lower temperatures. The nucleation layer can also be used to control the grain sizes of the subsequent CVD Mo growth, and therefore controls the electrical resistivity of the Mo film.