Morphology control and hydrophilic modification are important strategies to improve the photocatalytic activity of polymers. In the present work, novel conjugated microporous polymers with hollow spherical structures (CMPs-HSs) are prepared using 1,3,5-triacetylene benzene and 2,8-dibromodibenzothiophene as monomers through Sonogashira−Hagihara crosscoupling reaction and hard template method. In order to improve the dispersibility of the as-prepared CMPs-HSs in water, the hydrophilic modification of the CMPs-HSs is performed based on the thiol-alkynes click reaction, and the corresponding hydrophilic modified polymer is denoted as CMPs-HSs-S. The band gaps of CMPs-HSs and CMPs-HSs-S are 2.15 and 1.96 eV, respectively. The photocatalytic degradation rate of CMPs-HSs-S to Rhodamine B (RhB 20 mg L −1 ) is 90% within 80 min, while the CMPs-HSs is only 59%. Under the same experimental conditions, the degradation rate of CMPs-HSs-S to methylene blue (MB 20 mg L −1 ) is 85% within 120 min, and the degradation rate of CMPs-HSs to methylene blue is only 41%. The results of photocatalytic experiments show that the photocatalytic performance of CMPs-HSs-S is significantly better than that of CMPs-HS, suggesting that hydrophilic modification is more conducive to the contact of CMPs-HSs-S with pollutants and the occurrence of a photodegradation reaction. In addition, the corresponding composite membrane materials (abbreviated as CCMPs-MHSs and CCMPs-MHSs-S) of the CMPs-HS and CMPs-HS-S were prepared by the method of carbonized treatment, and their solar-driven interfacial evaporation (SDIE) performance was also studied. Under 1 kW m −2 simulated sunlight irradiation, the solar evaporation rates of CCMPs-MHSs and CCMPs-MHSs-S are 1.38 and 1.41 kg m −2 h −1 and the photothermal conversion efficiencies are 81.5 and 84.6%, respectively. Therefore, considering the designable flexibility of CMPs, the CMPs-based novel materials have great application potential in the study of photodegradation of organic dyes, solar-driven interfacial evaporation, etc.