Recycled waste wood is being increasingly used for energy production; however, organic and metal contaminants in by-products produced from the combustion/pyrolysis residue may pose a significant environmental risk if they are disposed of to land. Here we conducted a study to evaluate if highly polluted biochar (from pyrolysis) and ash (from incineration) derived from Cu-based preservative-treated wood led to different metal (e.g., Cu, As, Ni, Cd, Pb, and Zn) bioavailability and accumulation in sunflower (Helianthus annuus L.). In a pot experiment, biochar at a common rate of 2 % w/w, corresponding to ∼50 t ha(-1), and an equivalent pre-combustion dose of wood ash (0.2 % w/w) were added to a Eutric Cambisol (pH 6.02) and a Haplic Podzol (pH 4.95), respectively. Both amendments initially raised soil pH, although this effect was relatively short-term, with pH returning close to the unamended control within about 7 weeks. The addition of both amendments resulted in an exceedance of soil Cu statutory limit, together with a significant increase of Cu and plant nutrient (e.g., K) bioavailability. The metal-sorbing capacity of the biochar, and the temporary increase in soil pH caused by adding the ash and biochar were insufficient to offset the amount of free metal released into solution. Sunflower plants were negatively affected by the addition of metal-treated wood-derived biochar and led to elevated concentration of metals in plant tissue, and reduced above- and below-ground biomass, while sunflower did not grow at all in the Haplic Podzol. Biochar and ash derived from wood treated with Cu-based preservatives can lead to extremely high Cu concentrations in soil and negatively affect plant growth. Identifying sources of contaminated wood in waste stream feedstocks is crucial before large-scale application of biochar or wood ash to soil is considered.