To verify the priming effects of Maillard reaction precursors on the microbial decomposition of rice straw at different incubation temperatures, the method of indoor incubation at a constant temperature was adopted. In the process, the addition of glucose, catechol or glycine solution alone or in mixed solution was conducted at incubation temperatures of 10 °C, 15 °C and 28 °C, respectively. The C content of humic-extracted acid (CHLE), humification index (the ratio of C content of humic-like acid to fulvic-like acid, CHLA/CFLA), ∆logK value of humic-like acid (HLA), and C content of humin-like acid (CHLu) were dynamically analyzed at 0, 30, 60, and 90 d, respectively. At the same time, the differences in the atomic ratio and FTIR spectra before and after incubation were systematically analyzed. The results showed that (1) the additions of glucose alone and mixed precursors were both beneficial to increasing the CHLE content at three tested temperatures, especially at two low temperatures (10 °C and 15 °C), and glucose alone manifested the most significant improvement in CHLE. In contrast, following the addition of glycine alone, the CHLE content decreased by 2.4% at 15 °C and 4.6% at 28 °C after incubation. (2) Glucose as the sole precursor was more beneficial to improving the quality of the humic substance (HS) at 28 °C, but only enhanced the condensation degree of HLA molecules at 15 °C. Compared with the results at 15 °C and 28 °C, the HLA molecules had the lowest condensation degree at 10 °C, regardless of whether a single precursor or mixed Maillard precursors were used. (3) After incubation, the amounts of N compounds in the HLA molecules decreased to varying degrees, especially at 28 °C. The O-containing functional groups, such as carboxyl groups, from HLA molecules decreased following the addition of a single precursor, while the mixed precursors resulted in an increase in O-containing functional groups. Increasing the catechol content directly enriched the unsaturated bonds of HLA. With the decomposition of rice straw, regardless of how the precursors were added, the polysaccharide content decreased to different degrees. The decomposition of polysaccharides in HLA was more temperature-sensitive, and an increase in temperature might encourage more polysaccharide consumption. Under each temperature, the molecular structure of HLA was simplified initially and then gradually became complex. Finally, the addition of glucose alone at 15 °C was more favorable for the complexity of HLA molecules, while at 28 °C, it could only alleviate the degree of simplification of the HLA molecular structure to a certain extent. (4) At the three tested temperatures, compared with the CK control, either one precursor or a mixture of three precursors could more effectively promote the decomposition of CHLu. Under the conditions of 10 °C and 15 °C, the addition of mixed precursors was more beneficial to the decomposition of CHLu, causing the CHLu content to decrease by 37.9% and 44.7%, respectively, followed by the addition of glucose alone.