An alternating deposition film of a copolymer of p-(hexaflouro-2-hydroxylisopropyl)-alpha -methylstyrene and styrene (PSOH) and poly(4-vinylpyridine) (PVP) was fabricated on the basis of hydrogen bonding between hydroxyl and a pyridine ring in chloroform. It is found that the selection of solvent is very important for successful preparation of a multilayer film on the basis of hydrogen bonding. A series of PSOHs with different contents of hydrogen-bonding donors were used to fabricate multilayer assemblies. The driving force for multilayer assemblies was identified by FTIR. Several factors, such as solvents, concentration, and content of hydrogen-bonding donors, were discussed, which influence greatly the deposition process and layered architectures.