ZnO nanowires having a diameter in the range of 15-40 nm and several tens of micrometers in length were grown on steel alloy substrates by the thermal evaporation technique without the use of any catalyst or additives. A detailed structural analysis revealed that the as-grown ZnO nanowires are single crystalline with wurtzite hexagonal structures and preferentially oriented in the c-axis direction. Origination of a strong and sharp Raman-active E2 mode at 436.6 cm.1 indicated that the grown ZnO nanowires have good crystal quality with the hexagonal wurtzite phase. Photoluminescence spectra also exhibited a sharp and strong peak in UV and a suppressed and weak band in the visible region, confirming the good optical properties and less structural defects for the deposited products. Additionally, a systematic growth mechanism is also proposed in detail to acquire a better understanding for the growth of nanowires on steel alloy substrate.