Pyrolyzed organic waste, also known as biochar, is commonly used as a soil amendment and has recently been promoted to remediate metal mine tailings by increasing substrate pH, enhancing water and nutrient retention, and reducing bioavailability of toxic metals. Bottom ash from bioenergy facilities can contain high levels of charcoal residue, and thus qualify as a type of biochar according to international standards; the availability of this material at low costs makes it of particular interest in the context of tailings remediation. Naturally recruiting vegetation is critical in areas of primary succession such as mine tailings, and thus understanding vegetation responses on these substrates is essential. We examined responses of naturally regenerated "volunteer" vegetation to additions of high‐carbon wood ash biochar at a range of application rates (from 0 to 30 metric tons [t]/ha) at two gold mine tailings sites in northern Ontario, Canada over a 2‐year period. Volunteer vegetation cover increased with biochar dosage, peaking at 10–20 t/ha. Wood ash biochar amendments altered substrate physical properties (pH, electrical conductivity [EC], bulk density, total carbon [TC], and nitrogen [TN]), but effects varied by site and with dosage. Substrate TC and EC increased significantly with dosage at both sites with highest measures detected in the 10–20 t/ha amendment range. Species composition showed site‐ and dosage‐specific responses to biochar additions; however, species accumulation curves consistently showed peak species richness at intermediate dosages in both sites and both years of growth. Observed changes in volunteer vegetation suggest that low to moderate dosage applications of high‐carbon wood ash biochar can be highly beneficial for revegetation of mine tailings, but that wood ash impurities can result in deleterious effects at high dosages. Results from these field experiments demonstrate the potential of wood ash in tailings restoration and incentivizes additional in situ experiments to further discern site‐specific mechanisms. [ABSTRACT FROM AUTHOR]