Aerobic composting of distilled grain waste (DGW) at different initial pH values adjusted by CaO addition was investigated. Three pH-adjusted treatments with initial pH values of 4 (R1), 5 (R2) and 6 (R3) and a control treatment (R0) with a pH value of 3.5 were conducted simultaneously. The results showed that R0 had an unsuccessful start-up of composting. However, the pH-adjusted treatments produced remarkable results, with a relatively high initial pH being beneficial for the start-up. Within 65 days of composting, the degradation of volatile solids (VS) and the physicochemical properties of R2 and R3 displayed similar tendencies, and both produced a mature end-product, while R1 exhibited a lower VS degradation rate, and some of its physicochemical properties indicated the end-product was immature. Quantitative PCR analysis of ammonia oxidizers indicated that the occurrence of nitrification during the composting of DGW could be attributed to the activity of ammonia-oxidizing bacteria.