The nickel phosphorous catalyst coating was studied on the E-glass fiber by electroless deposition using sodium hypophosphite as a reducing agent in alkaline medium. The effects of deposition time, deposition temperature, pH of the solution, and amount of stabilizer used in the solution on the coating efficiency were investigated by X-ray diffraction (XRD), energy dispersive X-ray analysis (EDAX), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and differential thermal analysis (DTA). The XRD indicates the presence of amorphous and crystalline phases of Ni and nickel-phosphorous (NiP). From TGA, it is evident that the NiP coating increases the thermal stability and magnetic properties of the glass fiber. The bath temperature of 80 °C, pH of 9 to 9.5, and stabilizer concentration of 25 g/l are optimum to get a good and uniform coating of NiP on glass fiber. Carbon nanotubes were successfully coated on NiP coated glass fiber at a temperature of 700 °C. © 2016 Informa UK Limited, trading as Taylor & Francis Group.