In the productive process of alloy materials, the change of element contents can significantly affect the quality and reliability of the products. The on-line monitoring techniques can determine the element contents of metallic materials in real-time, which can then guide their manufactureing processes and improve their quality and reliability. The normal techniques have limited penetration depth in the sample and are not efficient for volume analysis, which will affect the analytical accuracy. Prompt gamma-ray neutron activation analysis (PGNAA) is a non-destructive, high sensitivity and multi-elemental determination technique and can be used for bulk sample analysis. This work studied the feasibility of determination for metallic materials by using PGNAA. The metallic samples were analyzed by measuring prompt gamma rays produced by inelastic scattering of fast neutrons. A PGNAA system consisting of a D-T neutron generator, neutron reflector, collimator, high-purity germanium (HPGe) detector, and shielding was built and used for analysis of metallic materials. Firstly, Fe, Ti, Cr, Ni and Cu samples with various masses were conducted with the designed system. The prompt gamma rays of the elements were fitted using GAMMAFIT software to obtain the net areas of prompt gamma rays, and the response between sample mass and net peak area was analyzed. The non-linear response caused by variation of detection efficiency was corrected to obtain a calibration curve. A good linear relationship could be observed after correction. The mass detection limit of these elements was calculated, and the values were Fe (44 g), Ti (25 g), Cr (33 g), Ni (108 g) and Cu (72 g), respectively. Secondly, the determination of Fe and Cr of stain steel samples was studied by using the system. The calibration curves of Fe and Cr were obtained with the standard samples. An unknown sample was then measured and analyzed. The results were compared with the X-ray fluorescence (XRF) measurement data. The experimental data showed that the relative deviations of Fe and Cr obtained with the two methods were 4.08% and -2.97%, respectively. The results demonstrated that the PGNAA technique could be applied for determining many metals and alloys, which provides a basis for other metallic samples analyses.