Effect of solvent exchange, i.e., the sequential immersion in water, acetone, and DMAc on the pore structure of cellulose and its dissolution behavior in lithium chloride/N,N‐dimethylacetamide (LiCl/DMAc) was investigated by using size exclusion liquid chromatography (SEC), dynamic light scattering (DLS), and small‐angle X‐ray scattering (SAXS). In the SEC experiment, poly(styrene)s, diethyl phthalate, and acetone were used as probe solutes and 2‐butanone was used as an eluent. Capacity factor of these solutes in the solvent‐exchanged cellulose were larger than those in the untreated one. This was remarkable when diethyl phthalate and acetone were used as solutes. Since the molecular radii of these solutes were estimated to be less than 1 nm, it was shown that the solvent exchange increases the amount of pores within cellulose with the radii of less than 1 nm. In the SAXS experiment, structural difference between the solvent exchanged and the untreated celluloses was observed when the celluloses were immersed in acetone. Values of specific inner surface and average chord length calculated from SAXS profile showed that the amount of small pores was increased in the solvent exchanged cellulose. Considering the results from SEC, DLS, and SAXS measurements, facilitated dissolution of the solvent exchanged cellulose in LiCl/DMAc was attributed to the increase in the pores with the radii of less than 1 nm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3976–3984, 2007