Composting additives can significantly enhance green waste (GW) composting. However, their effectiveness is limited due to the short action duration of a single-period addition. Therefore, this study proposes that multi-period additive modes to prolong the action duration, expedite lignocellulose degradation, reduce composting time, and enhance product quality. This study conducted six treatments (T1–T6), introducing a compound additive (BLP) during the mesophilic (MP) and cooling periods (CP). Each treatment consistently maintained 25% total BLP addition of GW dry weight, with variations only in the BLP distribution in different periods. The composition of BLP consists of Wbiochar: Wlactic acid: Wpond sediment in a ratio of 10:1:40. Specifically, T1 added 25% BLP in CP, T2 added 5% in MP and 20% in CP, T3 added 10% in MP and 15% in CP, T4 added 15% in MP and 10% in CP, T5 added 20% in MP and 5% in CP, and T6 added 25% in MP. In this study, composting temperature, pH value, electrical conductivity, total porosity, the contents of lignin, cellulose, hemicellulose, and nutrient, scanning electron microscopy images, germination index, and the successions of different bacteria and fungi at the phylum and genus levels were detailed. Results showed T4 achieved two thermophilic periods and matured in just 25 days. T4 enhanced lignocellulose degradation rates (lignin: 16–53%, cellulose: 14–23%, hemicellulose: 9–48%) and improved nutrient content. The above results, combined with correlation analysis and structural equation model, indicated that T4 may promote the development of dominant bacteria (Proteobacteria, Firmicutes, Actinobacteria, Bacteroidetes) by regulating compost physicochemical properties and facilitate the growth of dominant fungi (Ascomycota and Basidiomycota) by modulating nutrient supply capacity. This ultimately leads to a microbial community structure more conducive to lignocellulose degradation and nutrient preservation. In summary, this study reveals the comprehensive effects of single-period and multi-period addition methods on GW composting, providing a valuable basis for optimizing the use of additives and enhancing the efficiency and quality of GW composting.