A wide variety of adhesives can be used to manufacture multilayer food packaging materials. Since these materials are usually in direct contact with the packed food, compounds from the adhesive may migrate into it. Therefore it is important to determine the composition of the adhesives used. The main aims of this work were to determine the compounds present in the adhesives used in the food packaging, to study their migration to food simulants and finally to use these data to test a mathematical tool designed for predicting migration to food from laminates containing adhesives. For this purpose a total of 45 market samples of multilayer materials (laminates and other glued materials) produced with 29 different adhesives were studied. A total of 55 different compounds were detected in these adhesives, 57% of these compounds migrated into a dry food simulant (Tenax®) through the food contact layer. These data were also used to compare it with the theoretically estimated migration of the adhesive compounds using “upper-bound reference” values for the diffusion and partition coefficients implied in a multilayer migration model. In 93% of the cases the estimated migration results met or exceeded the experimental ones. This is an important requirement for testing the applicability of these theoretical migration estimations for compliance decisions which aim to protect the consumer's health.