The objective of this study was to investigate the impact of microbial inoculation and non-inoculation on the transformation of organic components, humus synthesis, and metabolic pathways in kitchen waste composting systems. The results revealed that microbial inoculation promoted the degradation of organic components in the compost, accelerating the degradation of easily degradable carbohydrates during the heating phase and hemicellulose and cellulose during the cooling phase. Inoculation facilitated the production and conversion of polyphenols, reducing sugar, and amino acids, leading to a respective increase of 1.20-fold and 1.14-fold in the content of humic acids and humus compared to the control group. Further analysis demonstrated that inoculation enriched the presence of Bacillus, Lactobacillus, and Streptomyces during the heating phase while enhancing positive microbial interactions by 1.08-fold, thereby promoting the degradation and transformation of organic matter to facilitate humus formation. In contrast, inoculation suppressed the abundance of Pseudomonas and Oceanobacillus, thereby weakening the denitrification process. Moreover, inoculation enhanced the metabolism of carbohydrates and amino acids, promoting the polyphenol humification pathway and facilitating the formation of humus. These findings contribute to a better understanding of composting dynamics and provide insights for optimizing composting processes in the field of kitchen waste management and organic waste recycling.