Divalent (Me) ions substituted W-type hexagonal ferrites with chemical formula Ba0.5Sr0.5Co2− xMexFe16O27 (x=0, 0.5 and Me=Mn, Mg, Zn, and Ni) were prepared by sol–gel autocombustion method at 1300°C for 5h. Thermal and IR spectral studies were carried out by means of differential thermal/thermogravimetric analysis and Fourier transform infrared spectroscopy respectively. The microstructure was investigated by using the powder X-ray diffractometer and the field emission gun scanning electron microscope. The results showed that divalent ions substituted W-type hexagonal ferrites were single phase and appeared as hexagonal platelet-like shape which is better shape for microwave absorption. M–H loops of a selected sample were measured up to maximum applied field of 9T in a temperature range of 4.2–400K. The values of saturation magnetization were calculated by the law of approach to saturation. The room temperature value of coercivity is found to be a few oersteds which is favorable for EM materials. Based on the results of electromagnetic parameters, reflection losses were calculated which are found to depend on the thickness of the absorber.