Hydrogels based on poly(methyl vinyl ether-co-maleic acid) and Tween 85 were prepared for hydrophobic drug delivery. The hydrogels were synthesized following a simple procedure carried out in solid state. The process did not require the use of any solvent and, as it is based on an esterification reaction, no toxic by-products were obtained. The resulting hydrogels contained Tween 85 inside the structure and due to the amphiphilic nature of this compound, hydrophobic domains within the hydrogel structure were formed. The obtained hydrogels showed good swelling capacities ranging from 100% to 600%. The esterification reaction that took place between poly(methyl vinyl ether-co-maleic acid) and Tween 85 was confirmed by infrared spectroscopy. Hydrogels were loaded with a hydrophobic drug model, Curcumin (CUR), showing that the hydrogels were able to retain up to 36 mg of CUR per g of hydrogel. Additionally, the synthesized hydrogels provided in vitro sustained CUR release over periods of up to 30 days. Finally, and due to the mucoadhesive nature of the prepared materials, one of the hydrogels was tested in vitro as an oral drug delivery system. For this purpose, the selected material was milled into microparticles (45-90 µm diameter). The release of CUR from the microparticles was evaluated under simulated gastric and intestinal conditions. The microparticles were able to release their cargos in 7 h. However, further work is required to optimize this system for oral drug delivery applications.