Benzotriazole (BTRs) and benzothiazole (BTHs) derivatives are a group of high production volume chemicals with emerging health concern, which found in tea beverages raising potential risks for food safety and human health. The present work describes a simple method using a “green” deep eutectic solvent (DES) based-ultrasound-assisted liquid-phase microextraction (UALPME) to rapidly extract BTRs and BTHs from tea beverages, and then applying UHPLC-electrospray ionization (+)-quadrupole time-of-flight mass spectrometry for detection and quantification. To overcome the challenges related to different experimental conditions, a Factorial Multilevel Categoric Design and a Face Centered Central Composite Design were applied to screen and optimize the parameters for the DES-UALPME procedure, respectively. After optimization, the method was validated and shown to possess low limits of quantification (LOQs; 1.5–12 ng mL−1), high precision (3–13%), and satisfactory accuracy (65–107%). The developed method was then successfully applied for the analysis of some selected BTRs and BTHs in tea beverages.