The exploitation of unavoidable food supply chain wastes resulting from primary and secondary processing for chemicals, materials, and bioenergy is an important concept in the drive towards circular-based, resource-efficient biorefineries rather than petroleum refineries. The potential production of hydrogels (materials) from unavoidable food supply chain wastes, which are naturally rich in biopolymers such as cellulose, hemicellulose, pectin, and lignin, represents an interesting opportunity. However, these intertwined and interconnected biopolymers require separation and deconstruction prior to any useful application. Thus, this study aims to explore the formation of hydrogels from defibrillated celluloses (MW-DFCs) produced via acid-free stepwise microwave hydrothermal processing of blackcurrant pomace residues. Initially, pectin was removed from blackcurrant pomace residues (MW, 100–160 °C), and the resultant depectinated residues were reprocessed at 160 °C. The pectin yield increased from 2.36 wt.% (MW, 100 °C) to 3.07 wt.% (MW, 140 °C) and then decreased to 2.05 wt.% (MW, 160 °C). The isolated pectins were characterized by attenuated total reflectance infrared spectroscopy (ATR-IR), thermogravimetric analysis (TGA), and 13C NMR (D2O). The cellulosic-rich residues were reprocessed (MW, 160 °C) and further characterized by ATR-IR, TGA, and Klason lignin analysis. All the MW-DFCs contained significant lignin content, which prevented hydrogel formation. However, subsequent bleaching (H2O2/OH−) afforded off-white samples with improved gelling ability at the concentration of 5% w/v. Confocal laser microscopy (CLSM) revealed the removal of lignin and a more pronounced cellulosic-rich material. In conclusion, the microwave-assisted defibrillation of blackcurrant pomace, an exploitable unavoidable food supply chain waste, affords cellulosic-rich materials with the propensity to form hydrogels which may serve useful applications when put back into food products, pharmaceuticals, cosmetics, and home and personal care products.