Orange waste, generally discarded, is a source of many bioactive compounds that could be used for the development of high-value-added products in the food, cosmetic, and pharmaceutical industries. The objective of this study was to evaluate the influence of extraction method (automated Soxhlet extraction and temperature-controlled maceration), solvent system, and extraction time on the recovery of bioactive compounds from Valencia orange (Citrus sinensis) by-products. Proximate characterization of the dried orange residue (DOR) was performed prior to extraction. The type of solvent (ethanol and methanol), solvent:water ratio (50, 75, and 100%), and extraction time (60 and 120 min) were evaluated in terms of total extraction yield (TEY), total phenolic content (TPC), and antioxidant capacity determined by ABTS and DPPH assays, for each extraction method. ASE generally provided higher extraction yield and total phenolic content, particularly with 75:25 ethanol:water at 120 min, whereas TCM combined with methanol produced the highest antioxidant capacity. Extracts with up to 46.32% TEY, 5.57 mg GAE/g dm, and antioxidant capacities of 66.49 and 11.10 µmol TE/g dm determined by ABTS and DPPH assays, respectively, were obtained. The results demonstrated that Valencia orange by-products are a source of phenolic compounds and antioxidants with potential for product development across different industrial sectors.