<p>Solar-driven evaporation-adsorption for lithium extraction from seawater can improve the adsorption efficiency towards lithium ions, however, the fabrication of conventional solar-driven evaporation-adsorption materials offen suffers from secondary pollution. To address these issues, this study developed a biomass-based evaporation-adsorption material PVV@VLJ-LIS by synergistically utilising multiple components of <i>Vaccinium bracteatum Thunb.</i> leaves, enabling the integrated coupling of interfacial evaporation and selective lithium adsorption. A freezing and salting out strategy was employed to crosslink a poly(vinyl alcohol) hydrogel and a VLJ-modified titanium-based lithium-ion sieve on the evaporator surface, thereby achieving <i>in situ</i> self-assembly between the organic components from the leaves and the lithium-ion sieve. VLJ endows PVV@VLJ-LIS with broadband photothermal absorption and antibacterial activity, and simultaneously promotes interfacial Li⁺ diffusion kinetics. Meanwhile, P-VLR serves as a porous supporting framework, facilitating the fixation of the lithium-ion sieve and water transport. Under 1 sun irradiation, the PVV@VLJ-LIS evaporator achieved a photothermal evaporation rate of 1.61 kg/(m²·h) with an evaporation efficiency of 80%. Under 40 °C, an initial Li⁺ concentration of 100 mg/L, and pH 12, PVV@VLJ-LIS achieved an equilibrium Li⁺ uptake of 17.472 mg/g. Relative to dark conditions, the adsorption capacity increased by 104.3%, which was attributed to the photothermally driven interfacial heating and the enhanced lithium-ion migration. In addition, the as-developed multifunctional evaporator exhibited pronounced antibacterial performance, anti-oil fouling, mechanical stability, and effective salt rejection, indicating the broad application prospects of PVV@VLJ-LIS for simultaneous lithium extraction and seawater desalination in complex seawater environments.</p>