A validated solid-phase extraction procedure was developed in order to efficiently recover active pharmaceutical ingredients from room temperature ionic liquids (RTILs) followed by waste processing with the final objective of IL recycling. Three different imidazolium triflimide RTILs were independently applied as sample matrices. Analytes included cannabidiol, diclofenac, ibuprofen, naproxen, estrone and estradiol. Nine commercially available solid sorbents were tested for their analyte recovery and IL separation performance, with three sorbents being selected and applied for further detailed extraction experiments. Final results showed high recoveries for the extraction of cannabidiol (97.8%), analgesics (86.6–92.1%) and hormones (94.5–95.7%) with relative standard deviations between 0.6 and 2.2%. After analyte extraction, 93.3 to 96.5% of RTIL could be recycled, hereby exhibiting no significant evidence of residual contaminations. Preliminary tests on industrial hemp plants showed that the developed method can also be applied to real-world samples. Conclusively, this study not only presents the efficient recovery of analytes from imidazolium triflimide RTILs to achieve compatibility with certain analytical detection methods, but also creates the opportunity to sustainably utilize ILs in analytical sample preparation.