Chemically deposited nickel coatings possess superior tribological properties such as high hardness, good wear, and corrosion resistance. The quest for improved tribological performance has led to the design and selection of newer variants of these coatings. The present chapter deals with the development of Ni-P-W coating on mild steel substrate and the improvement of tribological characteristics through modification of the coating process parameters. Three coating process parameters, concentration of nickel source, concentration of reducing agent, and concentration of tungsten source along with the annealing temperature, are optimized for minimum friction and wear of the coating. Friction and wear tests are carried out in a multi-tribotester using block on roller configuration under dry conditions. Taguchi-based grey relational analysis is employed for the optimization of this multiple response problem using L27 orthogonal array. Analysis of variance shows that the concentration of nickel source, the interaction between nickel source concentration, and reducing agent concentration, and also the interaction between nickel source concentration and tungsten source concentration have significant influence in controlling the friction and wear behavior of chemically deposited Ni-P-W coating. It is observed that wear mechanism is a mild adhesive in nature. The structural morphology, composition, and phase structure of the coating are studied with the help of Scanning Electron Microscopy (SEM), Energy Dispersive X-Ray analysis (EDX), and X-Ray Diffraction analysis (XRD), respectively.