A new, reliable liquid chromatography/atmospheric-pressure chemical ionisation mass spectrometry (LC-APCI-MS) method was developed for the quantitative determination of food emulsifiers composed of mono- and diacylglycerols of fatty acids (E471 series) in complex food matrices. These additives are extremely interesting for the food industry because of their useful properties. Indeed, they improve the manufacture of products by acting as foams and creams stabilisers, crumb-softeners, or antistaling agents. The proposed method also allows us to qualitatively characterise new food emulsifiers composed of other acid esters of mono- and diacylglycerols (E472 series). The validation of the method was performed on blank minicake spiked samples for detection limits (reaching ppm levels), linearity, recovery, precision, and accuracy. The method was then successfully applied to commercial additives containing mixtures of emulsifiers, as well as to food products such as margarines and minicakes.