The dissolution of cellulose in tetrabutylammonium acetate (TBAAc)/dimethyl sulfoxide (DMSO) was studied combining experimental and simulation techniques. It was found that the dissolution limit at 40 °C corresponded to a molar ratio close to one acetate per cellulose anhydroglucose units. MD simulations suggested that the acetate ions bind to cellulose by dual hydrogen bonds. This effectively turns cellulose into a polyelectrolyte, attracting the bulky tetrabutylammonium (TBA+ ) counter ions, which prevent close contact between chains in the dissolved state. This hypothesis was tested by 1 Hand 13C-NMR spectroscopy, which confirmed that acetate forms hydrogen bonds to cellulose, and by diffusion NMR spectroscopy, which demonstrated a strong dynamic correlation between bound acetate and tetrabutylammonium in near-quantitative agreement with simulation. The present results suggest that offering hydrogen bonding to the acetate ions is the main driving force for dissolving cellulose and that the TBA+ counter ions form a diffuse layer around the acetate-decorated cellulose chains.