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In this work, several kinds of quaternary ammonium-based room-temperature ionic liquids (QA RTILs) are synthesized by alkylation and ion-exchange reactions for the rapid dissolution of cellulose. The applications of cellulose materials have been limited due to their poor solubility in conventional organic solvents, because of a high degree of structural regularity and a large number of hydrogen bonds. The prepared ionic liquids were identified by nuclear magnetic resonance, elemental analysis, and liquid chromatography-mass spectrometry. The results indicated that <i>N,N,N</i>-triethylhexan-1-aminium acetate (N₆₂₂₂OAc), tetrahexylammonium acetate (N₆₆₆₆OAc), and <i>N,N,N,N&#8242;,N&#8242;,N&#8242;</i>-hexaethyldecane-1,10-diaminium acetate (C₁₀(N₂₂₂OAc)₂) exhibited good cellulose-dissolution without any pretreatment. The regenerated cellulose films with a low degree of crystallization of the cellulose II phase were also prepared easily in this process using N₆₂₂₂OAc due to its polar and small cation. These QA RTILs can be used as non-derivatizing solvents for cellulose and can also be easily recycled because of their thermostable and nonvolatile properties.