When growing one-dimensional (1D) nanomaterials via the vapour–liquid–solid (VLS) model, the substrates usually need to be coated with a layer of catalyst film. In this study, however, an effective approach for the synthesis of boron nitride (BN) nanowires directly onto commercial stainless-steel foils has been demonstrated. Growth occurs by heating boron and zinc oxide (ZnO) powders at 1100 °C under a mixture of nitrogen and hydrogen gas flow (200 ml min−1). The stainless-steel foils played an additional role of catalyst besides substrate during the VLS growth of these BN nanowires. The as-synthesized nanowires emit strong photoluminescence (PL) bands at 515, 535 and 728 nm. In addition, we found that the gas flow rate and the hydrogen content in the gas mixture strongly affected the diameter and yield of the nanowires by changing the relative concentration of the nanowire growth species in the chamber.