The average molecular weight of cellulose derived from filter paper, poplar, and Avicel decreases by up to two orders of magnitude during typical mild dissolution protocols using ionic liquids (ILs). About an order of magnitude greater cellulose depolymerization rate during ionic liquid dissolution occurs in 1-butyl-3-methylimidazolium chloride (BmimCl) and 1-ethyl-3-methylimidazolium chloride (EmimCl) compared to 1-ethyl-3-methylimidazolium acetate (EmimOAc), and, unintuitively, greater IL purity results in greater cellulose depolymerization. The following data support the mechanism of cellulose hydrolysis to be acid-catalyzed: (i) increase in number of reducing ends following cellulose dissolution in IL; (ii) addition of N-methylimidazolium base suppresses cellulose depolymerization during dissolution in IL; (iii) small amounts of glucose and traces of hydroxymethyl furfural are present following cellulose dissolution in IL. The acid is presumably synthesized via IL decomposition to generate a carbene and proton, consistent with hypothesis derived from molecular modeling. Titration experiments conducted here measure the amount of acid synthesized to be in the 4000 ppm range for high-purity BmimCl IL during mild processing conditions for cellulose dissolution. This data is relevant for understanding the extent of IL decomposition during biomass dissolution.