New molecular systems based on donor/acceptor groups connected by π-conjugated bridge, trans-[MoF(NNC₇H₆SO₂)(Ph₂PCH₂CH₂PPh₂)₂][BF₄], have been synthesized. This complex with nonlinear optical (NLO) applications was immobilized by an adsorption process from liquid phase, in the interlayer of a pillared clay (PILC). The metal complex and the new materials were characterized by thermal analysis (DSC), chemical analysis, surface techniques (XPS), X-ray powder diffraction (XRD), nitrogen adsorption isotherms, spectroscopic methods (NMR, FT-IR and UV/Vis) and electrochemical measurements. The studies of the electrochemical and the spectroscopic properties of the complex show interactions between donor and acceptor groups across the conjugated bridge. The results obtained from the studies using different techniques of analysis confirm that the molybdenum complex was effectively immobilized in the host matrix and this process does not modify the morphology or structure of the PILC upon metal complex loading.