Soluble coffee and coffee substitutes' consumption has grown considerably in recent years. These
products, prepared from roasted coffee and/or cereal extracts, are more consumer-friendly than plain
coffee, being usually cheaper. During roasting, several toxic compounds can be produced from carbohydrate
degradation in presence of aminoacids, including 4-methylimidazole (4-MeI). This work aimed
to screen the presence of 4-MeI in soluble coffee and its surrogates commercialized in Portugal using a
previously validated gas chromatography-mass spectrometry (GCeMS) method. In a total of 45 soluble
samples analyzed, including 10 plain coffees, 8 decaffeinated coffees, 12 cereal mixtures with coffee and
15 cereal mixtures without coffee, all the samples were positive for 4-MeI, with levels that ranged from
136 to 1411 mg/kg. All cereal-containing samples had significantly higher amounts (p < 0.01) than coffee
samples, whilst no statistical differences were observed between decaffeinated and plain coffees. The
high variability observed between samples is not influenced by the “brand” effect as well as by rawmaterial.