A new method based on off-line coupling of LC with GC in replacement of conventional sample preparation techniques is proposed to analyze acrylamide in coffee brews. The method involves the preseparation of the sample by LC, the collection of the selected fraction, its concentration under nitrogen, and subsequent analysis by GC coupled with MS. The composition of the LC mobile phase and the flow rate were studied to select those conditions that allowed separation of acrylamide without coeluting compounds. Under the conditions selected recoveries close to 100% were achieved while LODs and LOQs equal to 5 and 10 μg/L for acrylamide in brewed coffee were obtained. The method developed enabled the reliable detection of acrylamide in spiked coffee beverage samples without further clean-up steps or sample manipulation.