Breakfast cereals are significant contributors to the daily intake of food-derived acrylamide in Western countries. Acrylamide was determined by LC-MS in 60 commercial breakfast cereals marketed in Spain. Several SPE cartridges were evaluated for clarification of the aqueous extract. LOQ was 62 μg/kg. Acrylamide content ranged from <62–803 μg/kg (average 292 μg/kg, and median 258 μg/kg, with an estimated acrylamide intake from breakfast cereals of 2.68 μg acrylamide/person/day. According to the German concept of minimization, a signal value 450 μg/kg was calculated. Relationships among acrylamide and some parameters of the studied samples such as type of cereal, its physical form (puffed and flaked) or certain ingredients in the formulation (proteins and dietary fibre content) were also investigated. Wheat-based cereals contained significantly higher levels of acrylamide, as did samples with higher fibre or protein content. In addition, puffed breakfast cereals also contained significantly higher levels of acrylamide. There was no significant correlation between acrylamide levels and contents of 5-hydroxymethylfurfural, furosine or cereal browning.