The mechanical properties of self-supporting films based on starch-plasticizer and starch-PVOH-plasticizer and the barrier properties of paperboard coated with solutions of these polymers have been studied. The plasticizers used were glycerol, polyethylene glycol and citric acid. It was shown that the addition of a plasticizer and PVOH to starch substantially increases the flexibility of starch films. It was seen that curing the self-supporting films led to a decrease in flexibility. After heat-treatment, a substantial increase in storage modulus was observed only in the starch-PVOH-citric-acid blend films. Tensile tests on the films indicate that citric acid did not cause any noticeable phase separation. Citric acid acted as a compatibilizer for starch-PVOH blends even though a similar enrichment of PVOH at the air-solid interface was observed with both citric acid and polyethylene glycol as plasticizer. The properties of barrier coatings greatly reflected the compatibility of starch-PVOH blends containing citric acid. The only plasticizer that resulted in a lower water vapour transmission rate through the starch and starch-PVOH coatings was citric acid, which suggests that cross-linking took place. With four layers, coatings based of starch-PVOH possessed the same oxygen- transmission rate with citric acid as without citric acid.