The solar-driven interfacial evaporation (SDIE) technology serves as a clean and facile approach combining seawater desalination to address water shortage and energy crisis. Recently, porous organic framework materials have aroused great attention, and the development of MOF-based composites with significant performance in photothermal conversion and water activation has become one of the important focuses in this field. In this work, an MOF-based composite photothermal membrane (PON@MOF) was prepared via the in situ growth of metal−organic framework (MOF) nanoneedle arrays induced by a pyridine-based organic polymer nanowire network (PON). The PON@MOF membrane possessed an MOF array layer, a PON-induced layer, and a porous support layer. The PON is rich in coordinated nitrogen atoms for anchoring the metal-ion source, and the main role of the PON layer is to provide favorable nucleation sites and orient in situ growth of well-aligned MOF nanoneedle arrays. With the highly conjugated framework of PON@MOF and the light trapping of the nanoarrays strengthening the photothermal conversion as well as the hydrophilic chemical structure facilitating the decrease of the water evaporation enthalpy, the PON@MOF membrane realizes highly efficient thermal vapor conversion. Under solar irradiation (1.0 kW m −2 ), PON@MOF demonstrated an evaporation rate of 2.14 kg m −2 h −1 and a solar-to-vapor conversion efficiency of 98.5%. Meanwhile, the PON@ MOF membrane has excellent salt resistance and stability, highlighting its potential application in desalination. Overall, this work provides a special idea for the structural design of photothermal composites for solar desalination and freshwater production.