A new extraction phase based on hydrogel disks of polyvinyl alcohol (PVOH) and pectin was proposed, characterized and evaluated for the extraction of six steroidal hormones (estriol, estrone, 17β-estradiol, 17α-ethinylestradiol, progesterone, and testosterone) in aqueous samples with subsequent determination by gas chromatography-tandem mass spectrometry (GC-MS/MS) after the derivatization procedure. The developed extraction procedure was based on the solid phase extraction (SPE) technique, but employed hydrogel as the sorbent phase. The effects of several parameters, including the amount and composition of the sorbent phase, pH, sample volume, flow rate, and gel swelling over the extraction efficiency, were evaluated. Gels with lower swelling indexes and larger amounts of sorbent ensured higher extraction yields of analytes. The main benefits of using the PVOH/pectin-based hydrogel as the extraction phase are the ease of synthesis, low-cost preparation, and the possibility of reusing the extraction disks. Limits of quantification of 0.5 μg L−1 for estrone and 17β-estradiol, and 1 μg L−1 for testosterone, 17α-ethinylestradiol, progesterone, and estriol were obtained. Accuracy values ranged from 80% to 110%, while the inter-assay precision ranged from 0.23% to 22.2% and the intra-assay from 0.55% to 12.3%. Since the sorbent phase has an amphiphilic character, the use of hydrogels is promising for the extraction of medium-to-high polarity compounds.