In order to accelerate composting efficiency, municipal solid wastes (MSW) composting was conducted using three stages inoculation controlled by temperature (TSCT). At different composting phases, the samples were taken for the determination of organic matter transformation. Compared to routine inoculation method (CK), total organic carbon (TOC), dissolved organic matter (DOM) of TSCT decrease by 6.37%, 6.57%; and humic substance (HS), humic acid (HA), and humification index (HI) of TSCT increase by 8.61%, 16.75%, 18.40% at 336 hours of composting, respectively. Elemental analysis indicates C/H, O/C of HA molecule in CK increase by 8.33%, 6.25%; and those of TSCT increase by 18.33%, 11.48% at final stage of composting, respectively. These results all lead to the similar conclusion that TSCT would accelerate humification degree, and increase the efficiency of composting.