Atmospheric water harvesting has attracted much attention because of its potential to escalate the global freshwater shortage. However, the water collection efficiency is hindered by the trade-off between fast droplet nucleating and rapid droplet dripping due to the opposite requirements in the chemistry and the morphology of surfaces. Herein, the hierarchical porous composite film (ZIF-8@PVDF/PMMA, HPCF) with superhydrophobicity is designed for highly efficient and stable water harvesting. It indicates that the HPCF film has a large water contact angle (WCA) of 155.50° and ultralow sliding angle (SA) of 2°, exhibiting the self-cleaning function. Significantly, it is demonstrated that the water collection efficiency of HPCF can achieve 1.13 g·cm-2·h-1, which is much higher than the value of the blank sample, as well as most of the reported values. It is attributed to the hierarchical porous structure with the ZIF-8 crystals enhancing the surface roughness and endowing the film with the hydrophilic/superhydrophobic regions. This design promotes an optimal balance between droplet nucleation and shedding, significantly enhancing the water harvesting efficiency. Consequently, this work introduces an effective approach for water collection materials suitable for fog/mist conditions and provides an effective solution for the foggy area with water scarcity, demonstrating significance for advancing research aimed at mitigating the worldwide water shortage.