Electroless Ni–P films were deposited on mild steel substrate and sodium dihydrogen phosphite was used as a reducing agent. Temperature and pH of the bath were maintained at 90 °C and 6.86 to 10.86 respectively. The Ni–P film deposited samples were characterized by FE-SEM to know the surface and cross-section morphology of the film and the phases present were examined by X-ray diffraction. The chemical composition of the electroless Ni–P films was determined by EDS analysis. The thickness of the film was determined by FE-SEM cross-section image and was nearly 5 μm. The influence of pH values on film morphology was studied. Ni–P film was obtained in the pH ranges between 6.86 and 10.86 on mild steel substrate. Ni content in the film increased with increasing pH value of bath solution. Dense, uniform and small spherical shape grains were found in Ni–P film deposited at pH = 10.86. X-ray analysis shows a (222) preferential growth in all the films. The mean crystallite size of Ni–P films deposited at pH 6.86, 7.86, 8.86, 9.86, and 10.86, calculated by using the Scherrer-equation was found to be 44.7, 40.4, 41.2, 34.6 and 30.4 nm, respectively.