The effects of N-(2-hydroxyl)-propyl-3-trimethylammonium chitosan chloride (HTCC) on the physicochemical properties of sodium carboxymethyl cellulose (CMC)-based films were investigated. The prepared HTCC/CMC film-forming solutions (FFSs) with varying mass ratios exhibited shear-thinning behavior and typical pseudo-plasticity. The highest apparent viscosity and lowest crossover frequency was obtained for the HTCC/CMC FFS with a mass ratio of 10%, due to the formation of the strongest intermolecular interactions, which also led to the best mechanical properties. Furthermore, the effects of temperature and degree of substitution of HTCC on the composite film properties were also investigated. Structural property assessment by FTIR, SEM, and DSC showed a clear interaction between HTCC and CMC, leading to the formation of a new composite material with enhanced physicochemical properties. The data demonstrate the importance of HTCC in CMC-based films for food and drug packaging.