The rocketed development concerning electro-optic polymers fundamentally motivated by its pragmatic application in envisioning second-order nonlinear optics and waveguiding are cardinal. Modern synthetic strategies consigned an outstanding optical quality amorphous polymers with enhanced properties. Documented data revealed a huge progress in understanding their implementation, however challenges still exist regarding their temporal stabilities etc. This review delivers a brief investigation of nonlinear optical (NLO) polymer materials demonstrated over previous decades. Besides, their categorical explanation along with their structural architecting via engineering polymeric backbone or functionalization of the molecular entities have been reviewed. Correspondingly, their temporal and thermal stabilities accompanied by NLO characteristics features are also discussed.