<p>Freshwater scarcity poses an escalating threat to global sustainability, yet sorption-based atmospheric water harvesting offers a compelling solution by extracting moisture directly from air, independent of geographic constraints. A critical bottleneck limiting sorption-based atmospheric water-harvesting capacity, however, remains the sluggish kinetics of sorption–desorption cycling. While traditional strategies attempt to address this through single-scale macropore or air-duct engineering, they fail to achieve the multiscale transport regulation necessary for rapid water production. Here we report a heat-post-process-assisted three-dimensional printing strategy to fabricate a multiscale aluminophosphate fractal framework with hierarchical porous structures. This approach enables synergistic water transport across multiple scales: heat-activated pores at the nano- and microscales facilitate rapid intracrystalline and intercrystalline diffusion, while optimized fractal channels at the macroscale minimize surface mass-transfer resistance. Consequently, the framework exhibits sorption–desorption kinetics ten times faster than state-of-the-art sorbents. Leveraging this material, we demonstrate a scalable sorption-based atmospheric water-harvesting device utilizing multiscale aluminophosphate fractal frameworks with hierarchical porous structure arrays that achieves exceptional water productivity of 3.77–5.20 l_water kg_sorbent⁻¹ d⁻¹. This multiscale design paradigm provides a robust pathway for the development of high-performance, scalable water harvesting technologies.</p>