This study aims to improve the thermal stability and mechanical properties of carboxymethyl bacterial cellulose (CMBC) composite films. Experiments were conducted by preparing bacterial cellulose (BC) into CMBC, then parametrically mixing sodium alginate/starch/xanthan gum/gelatin and glycerin/sorbitol/PEG 400/PEG 6000 with CMBC to form the film. Scanning electron microscopy, X-ray diffractometry, infrared spectroscopy, mechanical tests, and thermogravimetric analysis showed that the composite films had better mechanical properties and thermal stability with the addition of 1.5% CMBC (% v/v), 1% sodium alginate, and 0.4% glycerin. Tensile strength was 38.13 MPa, the elongation at break was 13.4%, the kinematic viscosity of the film solution was 257.3 mm2/s, the opacity was 4.76 A/mm, the water vapor permeability was 11.85%, and the pyrolysis residue was 45%. The potential causes for the differences in the performance of the composite films were discussed and compared, leading to the conclusion that CMBC/Sodium alginate (SA)/glycerin (GL) had the best thermal stability and mechanical properties.