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To search for more high-performance crystalline proton conducting materials and to accelerate the related research progress, in this paper, a one-dimensional coordination polymer (CP), [Co(BBOT) 2 (H 2 O) 3 ·2H 2 O] n (1) (H 2 BBOT = N-benzoyl-N′-(4-benzoxy)thiourea) was firstly prepared by solvent volatilization approach. Subsequently, the thermal, H 2 O and chemical stabilities of the CP were tested and its high structural stability was confirmed. Furthermore, in 1 , a stable solid three-dimensional framework can be constructed by intermolecular H-bonds and stacking interactions between phenyl units. Then, utilizing the AC impedance determination, the dependence of the proton conductivity of this CP on temperature and humidity in the water vapor environment was explored and the positive correlation was verified. Excitingly, the optimized proton conductivity of this compound under specific test conditions (100 °C/98 % relative humidity) can be as high as 10−4 S/cm, being in the forefront of similar crystalline solid materials. Finally, according to the value of activation energy and the characteristics of crystal structure, we speculate on the proton conduction mechanism. Proton conductivity of a CP under variable humidity and temperatures was explored. Its highest proton conductivity can attain up to 10−4 S/cm, and its proton-conduction mechanism was speculated. [Display omitted] • One carboxylate-based Co(II) coordination polymer was prepared. • Its structure was characterized by single-crystal X-ray diffraction. • Its water-assisted proton conduction was explored. • The proton-conducting mechanism was speculated. [ABSTRACT FROM AUTHOR]