Most previous researches focused on small casting ingots prepared by arc melting, when studying high-entropy alloys. Large sized ingots were also necessary in exploring the existence of volume effects in the multi-principal element alloys. During the experiments, a large sized CoCrFeNiTi0.5 alloy casting ingot was prepared by a medium frequency induction melting furnace. A slight volume effect occurred, reflecting mainly in the growth of crystalline grains and the increase of alloy hardness in the ingot. To investigate the effect of annealing temperature on microstructure and properties of CoCrFeNiTi0.5 alloy, several samples taken from the ingot were annealed at 600 °C, 700 °C, 800 °C and 1000 °C respectively for 6 h. Almost no effects were found to the crystalline structure and elemental distribution when the samples were annealed below 1000 °C. The crystalline structure of CoCrFeNiTi0.5 alloy was composed of one principal face-centered cubic (FCC) solid-solution matrix and a few intermetallic phases in the form of interdentrite. Dendrite contained approximately equivalent amount of Co, Cr, Fe, Ni and a smaller amount of Ti. When annealed below 1000 °C, the interdendrite stayed in (Ni, Ti)-rich phase, (Fe, Cr)-rich phase and (Co, Ti)-rich phase. After 1000 °C annealing, (Co, Ti)-rich phase disappeared, while (Ni, Ti)-rich phase and (Fe, Cr)-rich phase grew. The microhardness of the as-cast CoCrFeNiTi0.5 alloy was 616.80 HV and the macrohardness was 52 HRC. The hardness of the samples stayed generally unchanged after annealing. This indicated a high microstructure stability and excellent resistance to temper softening that the CoCrFeNiTi0.5 alloy exhibited.