A deep eutectic solvent (DES) based on choline chloride and imidazole (CCIMI) was investigated for swelling of cellulose fibers prior to mechanical disintegration into cellulose nanofibers (CNFs). The dimensions of the DES treated and washed fibers were investigated after various treatment conditions (time, temperature, and cellulose consistency) using DES based on choline chloride–urea (CCUrea) and pure imidazole as references. Even mild treatment conditions (15 minutes at 60 °C) with CCIMI increased the diameter of the fibers from 18.1 to 18.9 μm, and a maximum diameter of 19.9 μm was obtained after three hours at 100 °C. Overall, CCIMI resulted in a higher degree of swelling compared to both references. In addition, pure imidazole caused a decrease in the degree of polymerization of cellulose, whereas cellulose degradation in CCIMI was negligible. The mechanical disintegration of CCIMI-treated fibers resulted in the production of CNF films with very good mechanical properties—specific tensile strength and work capacity being over 200 kNm kg⁻¹ and 10 kJ kg⁻¹, respectively—whereas CNFs films produced using choline chloride–urea had notably lower values (182 kNM kg⁻¹ and 7 kJ kg⁻¹, respectively). In addition, CNF films exhibited good oxygen barrier properties, even at an elevated relative humidity level (80%). CCIMI could be recycled without any effect on the mechanical properties of CNF films. The results presented here indicate CCIMI is a highly efficient pretreatment media for swelling and further nanofibrillation of cellulose, even at mild treatment conditions.