Dicyclic polymers having theta- and manacle-constructions with olefinic groups at the designated positions have been synthesized through electrostatic self-assembly and covalent fixation using linear precursors having either a pendant or an inner olefinic groups. The formation of the two constitutional isomers having theta-and manacle-constructions has been confirmed by reversed-phase chromatography (RPC) coupled with the matrix assisted laser desorption/ionization time-of-flight (MALDI TOF) mass analysis and by the metathesis cleavage of the inner olefinic group included at the specific position of the two isomer frameworks.