Endocardiosis, a degenerative and dystrophic process affecting cardiac valves and described in many mammalian species, is characterized by the accumulation of glycosaminoglycans, in particular hyaluronic acid, in the extracellular matrix. The glycoprotein patterns of pig mitral valves in normal animals and animals affected by endocardiosis were investigated. A different N-linked glycosylation pattern of glycoproteins was detected in affected valves compared with normal ones. In either normal or pathological species, the detected N-linked glycans were of the complex type. However, in samples from affected valves, sialic acid showed a prevalence of the alpha 2,6 linkage to the galactosyl residue, whereas in normal samples the most frequent linkage was of the alpha 2,3 type. In normal valves, the majority of complex oligosaccharides presented two outer branches with different degrees of fucosylation and sialylation, whereas in pathological samples we noted an increased number of glycans having up to four outer branches.