Zr(BH)·8NH is considered to be a promising solid state hydrogen-storage material, due to its high hydrogen capacity and low dehydrogenation temperature. However, the possible applications of Zr(BH)·8NH have been greatly hampered by the complicated and less applicable synthesis process, which must be operated at relatively low temperature (<20 °C). Herein, we reported a simple and facile “heating-(ball milling) BM vial” method via physical vapour deposition to tackle this issue. By this technique, Zr(BH)·8NH was successfully synthesized. Furthermore, composite formation by adding 10 wt% NaBH to the as-prepared Zr(BH)·8NH was found to be able to lower down the dehydrogenation peak of Zr(BH)·8NH from 130 to 75 °C and more excitingly, the possible emission of BH and NH from dehydrogenation of only Zr(BH)·8NH was completely suppressed after addition of NaBH. This research presents a new hydrogen-storage system based on Zr(BH)·8NH+NaBH4 composite and it also implies a new development methodology of future hydrogen storage materials.