Biodegradable packagings are made by combination of several materials creating a multilayer with the properties needed. Each material, including the adhesive, could contain substances that could migrate to the food. In this work, gas chromatography coupled with mass spectrometry and ultra-high-pressure liquid chromatography coupled with quadrupole time-of-flight mass spectrometry were used to identify the biodegradable adhesive compounds. Five of the 13 compounds identified were nonintentionally added substances; they were neoformed compounds created by the reaction of added compounds in the adhesive. Moreover, the migration of the compounds through four different biodegradable materials—paper, polylactic acid, ecovio®, and polyvinyl alcohol—was studied for the first time. Three of the 13 compounds identified in the adhesive migrated from the adhesive to Tenax®, which was used as a solid food simulant. One of them, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, was an intentionally added substance, and the other two were 1,6-dioxacyclododecane-7,12-dione and 1,6,13,18-tetraoxacyclotetracosane-7,12,19,24-tetraone, which were nonintentionally added substances identified in this work. Higher migration values (ranging from 0.81 to 2.07 mg/kg) were observed for migration through ecovio® than through the multilayer made by combination of ecovio® and polyvinyl alcohol (0.07–0.39 mg/kg) owing to the barrier effect provided by polyvinyl alcohol. The migration values for migration through paper and polylactic acid were below the limits of detection. Learn more.