Chitosan-magnesium aluminum silicate (CS-MAS) nanocomposites can be used as matrix films for buccal delivery of nicotine (NCT). The objective of this work was to prepare NCT-loaded CS-MAS films with different mixing orders of the components and varying amounts of NCT, and to investigate the characteristics of the films obtained. Blending MAS and NCT in the first step caused greater %NCT retention in the films because the NCT-MAS complexes could be formed completely, leading to a decrease in NCT volatilization during film drying. Additionally, this film provided a lower burst and total release of NCT than those prepared using other mixing orders; however, an indifference in NCT permeation across the mucosa was observed. However, all mixing orders still provided features of the nanocomposite films, as revealed by PXRD. The higher amount of added NCT caused a decrease in %NCT retention because of the limitation of the MAS amount to form complexes with NCT. The release and permeation rates of NCT increased with increasing NCT content. Furthermore, the NCT-loaded CS-MAS films still exhibited mucoadhesive properties. These findings suggest that the mixing order and amount of NCT added are important parameters for fabricating CS-MAS nanocomposite films for buccal NCT delivery.