New two-dimensional porous covalent organic frameworks (PHTA) with imine linkers have been synthesized and effectively utilized as metal free catalytic system for the synthesis of urea derivatives from a wide range of isocyanates under inert atmosphere. The material has been thoroughly characterized using powder XRD, HRTEM, FESEM, BET, FT-IR, XPS and a structure-activity relationship has been established. The imine based covalent organic framework owing to its highly conjugated system permits superior conduction efficiency of carriers, thereby exhibiting better performance and exceptional reusability and selectivity (> 99%) towards generation of urea derivatives from the corresponding isocyanates. At room temperature the solvent free catalytic process under nitrogen atmosphere requires short range of reaction duration (2 h) to produce high yields (84–96%) of ureaderivatives from respective isocyanates. The catalytic route of urea synthesis in presence of organocatalyst PHTA is suitably described by theoretical calculations (DFT) method. The heterogeneity and recyclability nature of the catalyst is checked for five cycles and the obtained result portrayed its good catalytic effectiveness.