The electron shakeoff probability of 6Li2+ ions resulting from the β- decay of 6He+ ions has been measured with high precision using a specially designed recoil ion spectrometer. This is the first measurement of a pure electron shakeoff following nuclear β decay, not affected by multielectron processes such as Auger cascades. In this ideal textbook case for the application of the sudden approximation, the experimental ionization probability was found to be P(so)(exp)=0.02339(36) in perfect agreement with simple quantum mechanical calculations.