EE in O/W/O emulsions could be determined with rheological and NMR measurements. Accuracy was at 10% for the rheological and at 2% for the NMR method. Detection limit was found to be at 5% for the rheological and at 1% for the NMR method. Within the degree of accuracy, both measurement techniques rheometry and NMR show good agreement in terms of encapsulation efficiency EE determination. NMR and rheological data showed that significant amounts of inner O1 phase are lost after the second emulsification step. Only for double emulsions produced via stirring, EE values > 0% could be detected with EE being higher for an increased amount of hydrophilic emulsifier in the W-phase. O/W/O emulsions processed with the colloid mill had inner dispersed phase contents lower than the detection limit of the applied PFG-STE NMR method, which is φ ≈ 1%. The same counts for the rheometric measurements. Although droplet size ratios between inner and outer droplets were unfavourable and the amount of employed hydrophilic emulsifier was low, parts of the inner oil phase stayed encapsulated. Gelling of the water phase using the hydrocolloid pectin might have reduced droplet movement and thus coalescence but has to be the focus of future research.