We have investigated the dynamic rheological properties of concentrated multiple emulsions to characterize their amphiphile composition at interfaces. Multiple emulsions (W-1/O/W-2) consist of water droplets (W-1) dispersed into oil globules (O), which are redispersed in an external aqueous phase (W-2). A small-molecule surfactant and an amphiphilic polymer were used to stabilize the inverse emulsion (W-1 in oil globules) and the inverse emulsion (oil globules in W-2), respectively. Rheological and interfacial tension measurements show that the polymeric surfactant adsorbed at the globule interface does not migrate to the droplet interfaces through the oil phase. This explains, at least partly, the stability improvement of multiple emulsions as polymeric surfactants are used instead of small-molecule surfactants.