3-Monochloropropane-1,2-diol (3-MCPD) esters are a group of process contaminants formed during the refining of edible oils and fats. A method for the determination of 3-MCPD esters in such oils and fats based on large-volume injection–comprehensive gas chromatography–time-of-flight mass spectrometry (LVI–GC×GC–ToF MS) is presented. The simplified method for sample preparation consists of alkaline hydrolysis followed by extraction of 3-MCPD from the lipid matrix and derivatization using phenylboronic acid. The limit of detection was 0.8 μg kg−1, reported as free 3-MCPD. The repeatability was better than 2.7 % relative standard deviation for levels around 0.5 μg g−1 3-MCPD. The GC×GC–ToF MS system was shown to be stable over 100 analyses.