•Dairy manure biochar was more effective than rice husk biochar in removing Pb, Cu, Zn, and Cd.•Dairy manure biochar showed less competitive sorption of metals than rice husk biochar.•Precipitation with CO32- or PO43- was mainly responsible for the metal removal by the manure biochar.•Removal of metals by rice husk biochar was mainly due to their complexation with phenonic OH. Rice husk biochar (RHBC) and dairy manure biochar (DMBC) were prepared as sorbents for simultaneously removing Pb, Cu, Zn, and Cd from aqueous solutions. DMBC was more effective in removing all the four heavy metals than RHBC, with the removal capacities of above 486mmolkg−1 for each metal, much higher than those of RHBC (65.5–140mmolkg−1). RHBC showed stronger competition for metal removal than DMBC when the four metals coexisted, with Pb the least affected and Cd the most inhibited. When each metal was 1mM in the multi-metal system, the metal removal by RHBC was reduced by 38.4–100%, much higher than that reduced by 2–40.9% for DMBC. The stronger competition for metals removal by RHBC was due to the fact that all metals competed only for the ionized phenolic-O− groups, while the removal of metals by DMBC resulted not only from the complexation with ionized hydroxyl-O− groups but also from the precipitation of metals with CO32- and/or PO43- that were rich in DMBC, resulting in less competition. The different mechanisms for the removal of metals by the two biochars were evidenced by the instrumental analysis of XRD, FTIR, and SEM as well as chemical modeling of Visual MINTEQ. Results indicated the waste biomass can be converted into value-added biochar as sorbents for removal of heavy metals and the removal ability varies with different biochar feedstock sources where the mineral components such as CO32-, PO43- originated from the feedstock play an important role in the sorption nature of biochar.