Polyrotaxanes have attracted significant attention of scientific community and are being explored towing to its electro-optical properties. The orientation and the molecular structure of polyrotaxanes influence its final properties. Thus a, detail understanding of the structure of such compounds at the molecular level will provide an opportunity to further tune and optimize their properties. Here chemically polymerized polythiophene polyrotaxane i.e. Thiophene [2]Rotaxane which is the rotaxane like compound consisting of several macrocycle, was studied in the powdered form. This allowed us to investigate the molecular structure of polyrotaxane and to obtain the detail insights into its structure property relationship via solid state NMR. The as-obtained polymer has also been characterized via various other techniques including UV spectroscopy, solution NMR and so on. We elucidated the structure of the Thiophene [2]Rotaxane monomer remained intact even after polymerization.