Zwitterionic hydrogel, serving as carriers for hygroscopic salts, holds significant potential in atmospheric water harvesting. However, their further application is limited by structural collapse in high-concentration salt solution and poor photothermal conversion performance. Herein, the graded pore structure of poly-3-[dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azaniumyl]propane-1-sulfonate (PDMAPS) zwitterionic hydrogel/TpPa-1 covalent organic frameworks (COFs)/LiCl composite (named as PCL composite hydrogel) is proposed, which leads to the accelerated diffusion effect for water molecules. As a result, the vapor adsorption capacity of the optimal composite hydrogel (PCL-42) reaches 2.88 g g-1 within 12 hours under conditions of 25 ℃ and 90% RH. Simultaneously, the maximum temperature of PCL-42 composite could reach 53.9 ℃ after 9 minutes under a simulated solar intensity of 1.0 kW m-2, releasing 91% of the adsorbed water in 3 hours, providing a promising prospect for efficient solar-driven atmospheric water harvesting. One cycle could collect 7.55 g of fresh water under outdoor conditions, and the maximum daily water production may reach 2.71 kg kg-1. The reason lies in that TpPa-1 COFs lead hydrogel to form a gradient pore structure, which may accelerate the transport of water molecules, increase the loading capacity of LiCl and enhance the photothermal property.