Complexation of nicotine (NCT) and magnesium aluminum silicate (MAS) has been formed in the dispersions that required multiple preparation steps. In this study, physical blending was used to produce NCT–MAS complexes. NCT, a free-base liquid state form, was adsorbed onto the MAS granules, where the diffusion and intercalation of NCT molecules into the MAS silicate layers occurred. These processes required a minimum of the 7-d-resting period to reach NCT complete distribution. FTIR, XRD, and 29Si NMR suggest that NCT could interact with MAS via hydrogen bonding, water bridging, and ionic electrostatic force. The 12 % NCT–MAS complexes enabled a sustained release of NCT, after a 2-min burst, in pH 6 phosphate buffer through a particle diffusion-controlled mechanism. Buccal discs formulated with NCT–MAS complexes and sodium alginate (SA) as drug carriers and matrix former could control NCT released through drug diffusion and swelling-controlled mechanisms. NCT release and membrane permeation increased with increasing NCT–MAS complexes or decreasing SA concentration. All NCT–MAS-containing buccal discs exhibited mucoadhesive properties related to the swelling characteristics of SA and MAS. Conclusively, NCT–MAS complexes can be produced through an uncomplicated single-step blending process, and the complexes obtained presented a potential to serve as drug carriers in buccal matrix formulations.