The bulk Cd0.8Zn0.2S semiconductor compounds doped with different amounts of magnesium(Mg) have been synthesized by controlled co-precipitation method from aqueous solution containing cadmium acetate, zinc acetate and thiourea at 0.02 mol% of Mgx(x=0~50ml). The solution mixture was made alkaline by adding 25% of liquid ammonia. The structural and electrical conductivity properties of Cd0.8Zn0.2S:Mg samples have been studied using X-Ray Diffraction (XRD) and Electrical Conductivity Studies. The samples have polycrystalline nature with hexagonal structure observed in the XRD studies. The average crystalline size varied from 30 to 47 nm and also calculated lattice parameters. The low temperature electrical conductivity measurements of Cd0.8Zn0.2S: Mg compounds were studied in the range of 77-300K by Keithley electrometer. It is observed that the increase in Mg doping concentration will increases the electrical conductivity. The values of activation energy were estimated for all the samples and found that the maximum activation energy at lower temperature range is 69.27 meV.