Current wound care still lacks multifunctional dressings capable of providing both structural support and controlled therapeutic activity. Developing such materials requires polymer matrices with tunable physicochemical properties, achievable through the rational selection of components and modifiers. In this study, polymer composites based on poly(vinyl alcohol) (PVA) and carboxymethyl cellulose (CMC), modified with glycerol and montmorillonite (MMT), were synthesized using a novel and rapid preparation method aimed at producing structurally adjustable matrices. The obtained materials were characterized by FTIR, SEM, and AFM analyses. FTIR spectra confirmed the competitive role of glycerol in reducing cross-linking efficiency and the compensatory effect of MMT in enhancing molecular interactions and structural density. The interaction between the two modifiers resulted in hybrid structures with intermediate organization, neither purely crystalline nor amorphous. SEM imaging revealed that glycerol promotes porosity, while higher MMT content stabilizes the polymer matrix, enhancing surface homogeneity. AFM revealed that the average roughness (1 × 1 μm scans) increased from 0.98 μm (sample B7) to 5.30 μm (sample C7) after glycerol addition. In conclusion, obtained results demonstrate the synergistic and opposing roles of glycerol and MMT, ultimately enabling the design of multifunctional polymer composites and warranting further investigation through XRD, DSC, rheology, and swelling capacity analyses.