Materials based on PVDF with desirable and controllable features were successfully developed. The chemistry and roughness were adjusted to produce membranes with improved transport and separation properties. Membranes were activated using the novel piranha approach to generate OH-rich surfaces, and finally furnished with epoxy and long-alkyl moieties via stable covalent attachment. The comprehensive materials characterization provided a broad spectrum of data, including morphology, textural, thermal properties, and wettability features. The defined materials were tested in the air-gap membrane distillation process for desalination, and improvement compared with pristine PVDF was observed. An outstanding behavior was found for the PVDF sample equipped with long-alkyl chains. The generated membrane showed an enhancement in the transport of 58–62% compared to pristine. A relatively high contact angle of 148° was achieved with a 560 nm roughness, producing a highly hydrophobic material. On the other hand, it was possible to tone the hydrophobicity and significantly reduce adhesion work. All materials were highly stable during the long-lasting separation process and were characterized by excellent effectiveness in water desalination.