Even after remediation, mining impacted soils can leave behind a landscape inhospitable to plant growth and containing residual heavy metals. While phytostabilization can be used to restore such sites by limiting heavy metal spread, it is reliant on soil capable of supporting plant growth. Manure-based biochars, coupled with compost, have demonstrated the ability to improve soil growth conditions in mine impacted soils, however there is a paucity of information regarding their influence on resident microbial populations. The objective of this study was to elucidate the impact of these soil amendments on microbial community structure and function in mine impacted soils placed under phytostabilization management with maize. To this aim, a combination of phospholipid fatty acid (PLFA) and enzymatic analyses were performed. Results indicate that microbial biomass is significantly increased upon addition of biochar and compost, with maximal microbial biomass achieved with 5% poultry litter biochar and compost (62.82 nmol g−1 dry soil). Microbial community structure was impacted by biochar type, rate of application, and compost addition, and influenced by pH (r2 = 0.778), EC (r2 = 0.467), and Mg soil concentrations (r2 = 0.453). In three of the four enzymes analyzed, poultry litter biochar treatments were observed with increased activity rates that were often significantly greater than the unamended control. Overall, enzyme activities rates were influenced by biochar type and rate, and addition of compost. These results suggest that using a combination of biochar and compost can be utilized as a management tool to support phytostabilization strategies in mining impacted soils.