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The phase diagrams of the Li2MoO4-Na2MoO4 and Na2MoO4-K2MoO4 systems have been reassessed using differential thermal analysis together with high-temperature and room-temperature X-ray diffraction analysis. The results showed that the compound Li2MoO4·6Na2MoO4 did not exist; however, it confirmed the existence of the compound Li2MoO4·3Na2MoO4 in the Li2MoO4-Na2MoO4 systems. With regard to the system of Na2MoO4-K2MoO4, we could not confirm the results reported by Bukhanova who claimed that the system was eutectic type with 1∶1 and 1∶2 intermediate compounds, refuting the statement of Amadori who thought there was an apparent phase boundary at high temperature in α-solid solution region of the Na2MoO4-K2MoO4 binary system. The revised phase diagrams of these systems are illustrated in this article. These experimental results are in agreement with the computerized prediction using the support vector machine-atomic parameter method for the assessment of phase diagrams.