The N-linked sugar chains of alkaline phosphatases, purified from rat AH-130 hepatoma and from normal rat liver, were released quantitatively as oligosaccharides by hydrazinolysis and were labeled by reduction with NaB3H4. A comparative study of their structures revealed that following structural differences are induced by hepatocyte carcinogenesis: complex-type tetraantennary sugar chains and hybrid-type sugar chains appear; outer-chain moieties of the sugar chains of the hepatoma enzyme contain exclusively the Gal(Beta 1-4)GlcNAc groups (type 2 chains) but those of the normal enzyme contain other Gal(Beta 1-)GlcNAc groups and type 2 chains; and novel fucosylated high-mannose-type sugar chains are found in the oligosaccharides of the hepatoma enzyme.