To illuminate the interactions in N-[(2-hydroxyl)-propyl-3-trimethyl ammonium] chitosan chloride (HTCC)/sodium carboxymethyl cellulose (CMC) based films, the film-forming solutions were studied by rheology, and HTCC/CMC based films were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy and thermogravimetric analysis. The HTCC/CMC based film-forming solutions with glycerol (polyvinyl alcohol (PVA) and anthocyanin) showed shear-thinning behavior. The apparent viscosity of the HTCC/CMC/glycerol (PVA and anthocyanin) film-forming solutions decreased slower than that of HTCC/CMC film-forming solution, due to the electrostatic interaction between HTCC and CMC, and hydrogen bonding interaction between the two biomacromolecules and glycerol, PVA and anthocyanin, which resulted in the formation of three-dimensional networks. The anthocyanin with rigid molecular structure formed different three-dimensional matrix with HTCC/CMC, resulted in viscosity dominated film-forming solution. The pH affected the electrostatic interaction between HTCC, CMC, and anthocyanin through neutralizing –COO− groups, and temperature showed a synergistic effect on both electrostatic interaction and hydrogen bonding. The inter-molecular interactions resulted in the red-shift of typical absorption peaks, and the increase of initial decomposition temperature and decomposition enthalpy of HTCC/CMC based films. The homogenous and smooth surface, and the compact texture of HTCC/CMC based films confirmed the intermolecular interaction between HTCC, CMC, and PVA (glycerol and anthocyanin).