For the rapid and efficient determination of acrylamide in food products by HPLC-UV, an environmentally friendly analytical approach has been developed, including liquid-phase extraction and subsequent liquid–liquid microextraction using a deep eutectic solvent. To automate the procedure, the flow-through “lab in a syringe” method was used. Acrylamide is considered a potential endocrine disrupting chemical and its main source is fried foods, which are widely consumed by both children and adults. To extract and concentrate acrylamide, hydrophobic deep-eutectic solvents based on various carboxylic acids and natural terpenoids were studied for the first time. It was found that benzoic acid, as a precursor of the extraction solvent, promotes the transfer of hydrophilic acrylamide from the aqueous phase of the sample due to the interaction of carboxyl and amide groups. The procedure has been validated and used effectively to estimate acrylamide content in beetroot and corn chips. Under optimal conditions, the detection limit was 0.01 mg/kg. Unlike existing methods, the proposed method is fully automated, does not require hazardous organic solvents and additional derivatization stages, and at the same time allows the determination of acrylamide at a level below established standards.