(1) Background: Residue degradation plays a very important role in terrestrial ecosystems and residue mixing is the main factor affecting the degradation rates. However, in the agricultural systems, the effect of residue mixing on the degradation of pepper residues and the microbial community in pepper root residues is not clear. (2) Methods: In this study, we added different residues into soil by using double-layered nylon litterbags in culture bottles. The treatments including pepper root (P: Capsicum annuum L.), soybean [S: Glycine max (L.) Merr.] and maize (M: Zea mays L.) residue, as well as mixtures of soybean + pepper (SP), maize + pepper (MP), maize + soybean + pepper (MSP) mixtures. Litterbags were harvested after 7, 14, 28, and 56 days, respectively. Mass loss and nitrogen and phosphorus contents in pepper residue were quantified and bacterial and fungal community levels in pepper residues were analyzed using quantitative PCR and high throughput amplicon sequencing; (3) Results: The study showed that the mass loss and fungal community abundance of pepper root residue in mixtures were higher than P, except day 7. The phosphorus contents in MSP-P and MP-P were significantly lower than that for P at day 28 and day 56. Illumina MiSeq sequencing showed that the presence of maize residue significantly altered the microbial community composition of pepper root pepper. Day 56. (4) Conclusions: Our results suggest that residue mixing changed the microbial community abundance in pepper residue and promoted the degradation of pepper residues compared to pepper residue decomposition alone, especially for mixtures with soybean.