Procedures for the iodometric solid-phase spectrophotometric determination of nitrite and selenium( IV) using a polymethacrylate matrix are proposed. The procedures are based on the reaction of nitrite and selenium(IV) with iodine in an acidic medium with the release of free iodine in amounts equivalent to those of the substances to be determined, extraction of the iodine formed with a polymethacrylate matrix, and measurement of absorbance of the matrix at 370 nm. The developed procedures ensure the determination of 0.01–0.12 mg/L of nitrite and 0.05–0.40 mg/L of selenium(IV) with limits of detection of 0.005 and 0.03 mg/L, respectively. It was shown that the proposed procedures can be applied to the determination of selenium(IV) in mineral water and nitrites in vegetables and soil.