The most probable value theory has been applied to analytical radioassay for mixture samples of six pure-beta emitters by using a liquid scintillation spectrometer. Activities of each nuclide in the mixture sample can be determined by solving normal equations which are derived from twelve observation equations, the number of which is twice that of nuclides to be radioassayed. Requirement for the technique is to construct quenching correction curves of the respective nuclides. This technique has been tested to3H–63Ni–14C–45Ca–36Cl–32P mixture samples, and found to be very useful with the aid of computerized data processing.