An NACE method was developed for the quantitative determination of acrylamide in processed food. The method is premised on the modification of the aqueous acid-base character of acrylamide in an organic solution. Acrylamide, which is a polar molecule in aqueous solution, in a low-pH environment in ACN acquires a proton, and thereby migrates under its own electrophoretic mobility in CE. Thus, nonaqueous separation of acrylamide was achieved by employing 30 mmol/L HClO4 in ACN as the running electrolyte. The detection limit of the method for acrylamide was found as 0.041 mg/L using UV detection at 200 nm. The run-to-run and day-to-day precisions for the corrected peak areas were calculated as 1.65 and 3.90%, respectively. The applicability of the method has been demonstrated by analyzing acrylamide in the samples of potato chips and French fries. The method is simple, rapid, inexpensive, and widely applicable for the determination of acrylamide in food samples.