Well-defined multicyclic polystyrenes are prepared in two steps. The first step is the preparation of a cyclic difunctional polystyrene by the reaction of alpha,omega -dilithiopolystyrene chains with 1,3-bis(phenylethenyl)benzene. Then, this product is covalently grafted to poly(chloromethylstyrene) chains leading to the formation of a high molar mass product containing linear and cyclic parts. As a model reaction and to optimize the previous reaction, a study of coupling of the linear difunctional model polystyrene with poly(chloromethylstyrene) is performed leading to grafted polystyrene. The grafted products are analyzed by size-exclusion chromatography, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, and liquid chromatography at the exclusion-adsorption transition point.