This study has for the first time shown that complex food emulsifiers such as starch and protein can be applied to produce stable w/o/w emulsions with the membrane emulsification technology. Using a microporous metal membrane with a 20 pm pore size, 2% of polyoxyethylene (20) sorbitan monolaurate (Tween 20), 4% of octenyl succinic anhydride (OSA) starch or 1.5% of pea protein isolate (PPI) in the external water phase respectively was the minimum concentration necessary to stabilise the w/o/w droplets. Uniform with a span as low as 0.45 and for at least 13-day stable w/o/w emulsions of droplets between 35 and 320 mu m were obtained. The release of a magnesium tracer from the internal water phase of xanthan gum-thickened w/o/w emulsions, when OSA starch and PPI were used, was found to be limited to around 3% after 13-day storage. However, w/o/w emulsions stabilised with Tween 20 were less stable with magnesium showing a release of 27% on day 13.