A NaOH/urea (or thiourea) solvent system capable of dissolving cellulose at lower temperatures is a breakthrough in cellulose chemistry, and it was reported that cellulose rapidly dissolved when it was added to a precooled aqueous solution of sodium hydroxide (NaOH) and additives. Therefore, this work compared the effectiveness of the direct dissolution method and freezing-thaw method in dissolving pulp fiber and pure cellulose. Three aqueous solutions were examined: 7% NaOH/12% urea, 9.5% NaOH/4.5% thiourea, and 8% NaOH/8% urea/6.5% thiourea. The dissolving capacity of three NaOH/additives aqueous solutions was analyzed by polarized optical microscopy and the dissolved cellulose proportion was determined. The results showed that the never-dried softwood dissolving pulp and bamboo dissolving pulp achieved better dissolution using freezing-thaw method than using direct dissolution method in the three aqueous solutions. The dissolving method had a negligible effect on the dissolution of each dissolving pulp in the 8% NaOH/8% urea/6.5% thiourea solution. It seems that the direct dissolution method was more suitable for oven-dried microcrystalline cellulose with a low degree of polymerization (DP) and the freezing-thaw method was more suitable for never-dried pulp cellulose fibers with a higher DP.