During the preparation of W/O/W-type double emulsions, a part of the internal water phase is often released to the external water phase. Thus, it is important that the enclosed water volume fraction can be determined in a simple and straightforward manner after preparation. In this work, a method is developed to determine the enclosed water volume fraction of W/O/W-type double emulsions using analytical photocentrifugation after which the results are compared to the enclosed water volume fraction as determined using pulsed field gradient Nuclear Magnetic Resonance (NMR). From the results, it can be concluded that analytical photocentrifugation is indeed a simple and straightforward method to determine the enclosed water volume fraction of double emulsions.