The available literature and research work on W-type hexaferrites is mainly focused on Co- and Zn-based calcium W-type hexagonal ferrites with a variety of cationic substitutions. The Modifications in the properties of the Calcium W-type ferrite based on Ni²⁺ as the divalent metal ion, however, is not studied sufficiently in the research literature vailable. In this study, the focus is mainly on the effects of substitution of Ni²⁺ on the properties of CaCo₂W exaferrites. The investigations carried out are mainly XRD, SEM and VSM. The main objective of this research investigation is to study the effect of substitution of Nickel and Cobalt on the structural and magnetic properties of calcium W-type hexaferrite CaCo_2-xNi_xFe₁₆O₂₇ (x=0, 1 and 2). XRD analysis and characterization revealed slight decrease in the values of lattice constants ‘a’ and ‘c’ with increase in concentration ‘x’. The particle size was confirmed from SEM and TEM images. The analysis of VSM for magnetic properties reveals decrease in coercivity and increase in the values of saturation magnetization as concentration increases. The results of measurements made bythe various experimental techniques and the observations were compared to understand the crystalline and magnetic structure of the compounds