This study shows a one-pot route to open cellular and functional monoliths.An oil-in-water high or medium internal phase emulsion readily forms by dropping oil into a dispersion of microcrystalline cellulose (MC) in aqueous branched polyethylenimine (PEI) solution. Crosslinking of PEI followed by removing the volatile yields an open cellular monolith. The key point of this strategy is that PEI can act as an emulsifier at high pH and simultaneously as reactants and finally as absorbing component. Results show that the rigid MC skeleton is fully covered by the flexible PEI network. The active amine content of the monolith reaches up to 3.3 mmol NH per g monolith. The open-cellular structure stems from volume contraction. The porous monolith can sequester trace anionic dyes in water with an absorbing capacity up to 440 mg g À1 monolith, whereas the adsorption is highly charge-selective. The monolith is pHrecyclable and facilely separable from water.