Our recent NR experiment have shown some fascinating interplay between surfactants and plasticisers in PVA film, which leads to dramatic changes in the surface segregation of each component and has important implications for their application in encapsulating detergents and food products. Here we wish to go a stage further and address the synergy between surfactants in their adsorption on PVA film surfaces. While this behaviour is well established in aqueous systems, this has not been explored for surfactants in a complex polymer matrix. Since our earlier results show stark contrasts between the behaviour of surfactants in water and PVA, the results would not be trivial to predict. This work will be an important step in validating models for industrial use, which is a key goal of our wider research programme into molecular migration in complex and evolving polymer matrices.