Improving the recovery of organic matter and phosphorus (P) from hazardous biowastes such as swine manure using acidic substrates (ASs) in conjunction with aerobic composting is of great interest. This work aimed to investigate the effects of ASs on the humification and/or P migration as well as on microbial succession during the swine manure composting, employing multivariate and multiscale approaches. Adding ASs, derived from wood vinegar and humic acid, increased the degree of humification and thermal stability of the compost. The 31P nuclear magnetic resonance spectroscopy and X-ray absorption near-edge structure analyses demonstrated compost P was in the form of struvite crystals, Ca/Al-P phases, and Poly-P (all inorganic P species) as well as inositol hexakisphosphate and Mono-P (organophosphorus species). However, the efficiency of P recovery could be improved by generating more struvite by adding the ASs. The flows among nutrient pools resulted from the diversity in the dominant microbial communities in different composting phases after introducing the ASs and appearance of Bacillus spp. in all phases. These results demonstrate the potential value of ASs for regulating and/or improving nutrients flow during the composting of hazardous biowastes for producing higher quality compost, which may maximize their beneficial benefits and applications.