The effect of ultrasound on gas-diffusion and pervaporation flow injection separation was investigated. Ammonia and three aliphatic amines (propylamine, tri-ethylamine and di-n-butylamine) with different volatility and surface activity were used as model analytes. Under the experimental conditions used, sonication did not enhance gas-diffusion separation efficiency and resulted in up to 62% improvement in pervaporation mass transfer. Based on these findings and taking into account the surface activity of the analytes studied which decreased with their molecular mass it was postulated that ultrasound-induced surface rippling was primarily responsible for the enhanced evaporation in the donor chamber of the pervaporation cell. The results reported in this paper suggest that ultrasonic pervaporation separation could extend the applicability of this on-line flow injection separation technique to the direct determination of higher molecular mass volatile and semi-volatile analytes in 'dirty' samples.