Based on molecular design,a novel biphenonl-like monomer 4-(4′-hydroxyphenyl)-2,3-phthalazin-1-one (DHPZ) was originally synthesized through simple reactions from phenol and phthalic anhydride which are common and easily available chemicals．The synthesizing processes,reaction dynamics and mechanism were studied in detail．According to a lot of experiments and computer-aided molecular simulation,it has been confirmed that this new compound has non-coplanar and twisted structure and the hydrogen atoms in N—H and O一H bonds show similar polycondensation reactivity,so it is proved to be a biphenol-like monomer．By solvent nucleophilic substitution polycondensation,a series of polymers such as poly(ether ketone)(PPEK),poly(ether sulfone)(PPES),poly(ether ketone ketone)(PPEKK),poly(ether sulfone ketone)(PPESK),poly(ether sulfone ketone ketone)(PPESKK),poly(ether nitrile ketone)(PPENK),poly(ether nitrile sulfone)(PPENS) and poly(ether nitrile sulfone ketone) (PPENSK),were successfully prepared from DHPZ,and commercial bihalogen monomers such as difluorodiphenylketone (DFK),dichlorodiphenylsulfone (DCS),[4-(chlorobenzoyl) phenyl]-(4-chlorophenyl) methanone (DCKK) and 2,6-dichlorobenzonitrile (DCBN)．The structures of these resultant polymers were characterized by spectroscopy,and the properties of these polymers were measured．Also the relationships between structures and properties were thoroughly studied．Spectroscopic data show that all these polymers are amorphous．The glass transition temperatures of all these polymers are in the range of 250℃ to 370℃,which can be controlled by the substituted groups or the proportion of the ketone and sulfone groups in the backbones of the polymers．Based on these results,a new molecular designing theory was put forward that introducing the non-coplanar twisted aramatic structure into polymers’backbones contributes to improving polymers’solubility and outstanding thermal resistance at the same time．Directed by this theory,a series of novel diamine,diacid and dianhydride monomers containing phthalazinone moities were successfully synthesized from DHPZ．And the corresponding polymers which have good solubility and outstanding thermal properties such as PPEA,PPEI,PPEAl were prepared．These polymers exhibit excellent comprehensive properties such as good solubility and outstanding thermal properties,forming a polymer system of new structure and high performance．