Engineered biointerfaces are crucial for many biomedical applications involving the interaction of (bio)materials with cells and tissue. Providing cues to support cell adhesion/proliferation in the form of biomolecules and/or by providing spatially controlled adhesive patches are important aspects. We demonstrate the assembly of composite films consisting of negatively charged liposomes (L ⁿ), poly(dopamine) or cholesterol-modified poly(methacrylic acid) (PMA _c) capping layers and (poly(l-lysine)/PMA _c) _x terminating multilayers. We show that hepatocytes adhere to the assembled composite coatings. Their association with fluorescent lipids from the film varies depending on the capping layer and cell adhesion time. This association was suggested to be an energy-dependent process. Further, the incorporation of paclitaxel (TX) into L ⁿ reduces the number of hepatocytes adhering to films without terminating multilayers. An exemplary composite coating is patterned, and the subsequent site-selective adhesion of hepatocytes is shown. For the first time, composite coatings to be used for substrate-mediated drug delivery with control over the positioning of the adhering cells are shown.