Biomass-fuelled facilities generate alkaline and mineral-/nutrient-enriched co-product (ash) that has to be appropriately managed, and preferably reused. The assumption that wood biomass fly ash (BFA) could be used in chemical amelioration of soil acidity and fertility was tested by: i) physicochemical characterisation of BFA and ii) bioassay with maize grown in acidic (pHKCl 4.68) hydromorphic soil amended with BFA (0–10% w/w). Scanning electron microscopy with energy dispersive X-ray spectroscopy and X-ray diffraction revealed non-homogeneous (ir)regular spherical/porous agglomerated particle morphology and distinctive distribution of Si-/Ca-/K-based minerals, while secondary ion mass spectrometry, for the first time, confirmed their isotopic (six Ca, three Si/Mg and two K isotopes) diversity. BFA addition strongly shifted soil pHKCl (up to 9.1), raised salinity (by > 8.2-fold) and the content of most phytonutrients (up to 5.4-fold); however, BFA amendments at >1.25% restricted the maize root and shoot growth, likely due to alkaline stress as indicated by necrotic/chlorotic symptoms at >5.0% rate. The BFA amendments increased total concentration of metals in soil (without exceeding the levels recognised as contamination); however, phytoextraction of Cd, Zn, Mn, Cu and Mo was significantly supressed (Cd by almost 12-fold), confirming that BFA improved soil-plant metal immobilisation, shifting rhizosphere biogeochemistry towards chemisorption/precipitation reactions. Even though results revealed a strong liming and P–K–Ca–Mg–Zn–Mn–Cu enrichment potential of BFA, to avoid possible negative environmental implications (saline/alkaline stress, metal contamination, adverse effects on soil microbiome), quantitative and qualitative ex ante evaluation of the BFA/soil matrix combinations is essential before application to ameliorate suboptimal (acidic, low-nutrient) or metal-contaminated soils.