A novel class of perfluorocyclobutyl (PFCB)-containing reactive polymer with adjustable phenolic hydroxyl contents (PFCB-OH-xx) has been developed. A serial of PFCB-OH-xx polymers with high molecular weights (M-w > 100,000) and narrow molecular weight distributions (M-w/M-n < 1.15), were facilely prepared from 2-methoxy-1,4-bis(trifluorovinyloxy)phenyl via thermal cyclopolymerization and demethylation reactions. The monomer and polymers were characterized by FT-IR and NMR spectra. PFCB-OH-xx polymers exhibit good thermal stability and excellent solubility in common organic solvents. Initial investigation of the use of PFCB-OH-xx polymers as precursors in post-functionalization of PFCB aryl ether polymers, was successfully accomplished by a nucleophilic ring-opening reaction between the phenolic hydroxyl groups and 1,3-propanesultone. The degree of functionalization can be readily controlled by adjusting the hydroxyl contents of PFCB-OH-xx polymers. This work demonstrates that the designed PFCB-OX-xx polymers could be a class of promising precursor for development of new functional PFCB aryl ether polymers. (C) 2016 Elsevier Ltd. All rights reserved.