Although solar steam generation strategy is efficient in desalinating seawater, it is still challenging to achieve continuous solar-thermal desalination of seawater and catalytic degradation of organic pollutants. Herein, dynamic regulations of hydrogen bonding networks and solvation structures are realized by designing an asymmetric bilayer membrane consisting of a bacterial cellulose/carbon nanotube/Co2(OH)2CO3 nanorod top layer and a bacterial cellulose/Co2(OH)2CO3 nanorod (BCH) bottom layer. Crucially, the hydrogen bonding networks inside the membrane can be tuned by the rich surface –OH groups of the bacterial cellulose and Co2(OH)2CO3 as well as the ions and radicals in situ generated during the catalysis process. Moreover, both SO42- and HSO5- can regulate the solvation structure of Na+ and be adsorbed more preferentially on the evaporation surface than Cl-, thus hindering the de-solvation of the solvated Na+ and subsequent nucleation/growth of NaCl. Furthermore, the heat generated by the solar-thermal energy conversion can accelerate the reaction kinetics and enhance the catalytic degradation efficiency. This work provides a flow-bed water purification system with an asymmetric solar-thermal and catalytic membrane for synergistic solar thermal desalination of seawater/brine and catalytic degradation of organic pollutants.