Solar-driven interfacial water evaporation has become one of the most promising approaches to effectively harvesting freshwater, yet the fabrication of high-performance and multifunctional solar interfacial evaporators (SIEs) still remains a huge challenge to date. In this study, a multifunctional MXene and Fe-MOF@cellulose acetate/polyvinylpyrrolidone (MXM@CP) SIE was prepared via a facile "electrospinning and suction filtration deposition" coupling strategy. Thanks to the incorporation of MXene, MXM@CP displayed excellent photothermal conversion performance. Together with the fast water transport channel provided by the porous cellulose acetate electrospinning substrate, a remarkable solar-driven water evaporation property was achieved for MXM@CP, showing a higher water evaporation rate of 1.1 kg m-2 h-1 under one sun irradiation. Moreover, the resultant composite film also exhibited excellent Fenton catalytic activity to effectively degrade volatile organic compounds (VOCs) due to the synergistic effect of the MXene and Fe-based MOF (Fe-MOF). Particularly, a relatively higher degradation rate of 82.8% was acquired for the resulting evaporator toward the benzene contaminant. These results provide new insights into the construction of high-performance and multifunctional SIEs toward clean freshwater collection from the VOC-contaminated water system.