The effects of the contents of NiSO4·6H2O, NaH2PO2·H2O, C2H5COOH and H3BO3, pH and temperature on electroless Ni–P alloy plating on quartz optical fiber surface were studied by orthogonal test, and the optimal values of the above six factors were determined as follows: 35 g/L, 32 g/L, 20 mL/L, 28 g/L, pH 5.0 and 84 °C. The surface morphology, composition and structure of Ni–P alloy deposit were characterized and analyzed by SM, ICP and XRD. The effects of the above process factors on the deposition rate of Ni–P alloy were discussed by single factor experiment and the kinetic model for Ni–P alloy deposition was established. The experimental results proved that the model is in good agreement with the experimental data, and can be applied to the process adjustment and product control of Ni–P alloy deposition on quartz optical fiber surface.