Design functionalized absorbent materials that fulfillment complex requirements in sophisticated water-treatment fields remains challenging. In this paper, a novel superhydrophobic/superoleophilic sponge with flower-like channel structures and a photodegradation functionality was fabricated via in-situ chelation of zinc oxide (ZnO) and nano-Ag particles. After low surface energy modification with POTS, the as-prepared sponge displayed remarkable superwettability, with a water contact angle (WCA) of 158.8° ± 1.3°. This endowed it with the ultrafast, selective absorption of diverse oils that are 33.9–135.2 times of their own weight. The prepared sponge’s emulsified oil separation efficiency can reach 99.87%, owing to its superhydrophobic/superoleophilic properties and the electrostatic attraction demulsification, guiding effect of ZnO layer crystal plane. Furthermore, the construction of Schottky barrier at the ZnO@Ag interface reduced the recombination rate of photoexcited electrons and electron-holes. Thereby, the prepared sponge’s photodegradation efficiency reached up to 97.07% after 4 h sunlight irradiation. Notably, the stress attenuation of the prepared sponge was only 14.6% after 100 absorption cycles, indicating its excellent mechanical stability. Moreover, the prepared sponge showed excellent environmental tolerance under severe conditions with its WCA stably exceeding 150.0°. Thus, this durable superwetting sponge can be effectively used for oil/water emulsion separation and organic pollutant degradation.