Insertion of silver tetracyanoquinodimethane (AgTCNQ) complexes into a Langmuir-Blodgett matrix is achieved by diffusion of silver nitrate into N-docosylpyridinium-TCNQ complex multilayers, followed by reaction of silver cations with the TCNQ species in situ. Formation of a new compound in the films causes a change in optical absorption related to charge transfer of TCNQ complexes and a chemical shift in binding energy for the core levels of silver and nitrogen incorporated in the TCNQ radical anion as well as an increase in thickness per layer by 2.5 angstrom of the films. The reaction rate is influenced by film reactivity, but is independent of the bulk solution concentration of silver nitrate, probably because of the limited diffusion of the molecules in compact films.