The similar flotability of scheelite, fluorite, and calcite resulted in the difficult separation by flotation. This work revealed the effect of water glass on the flotation of scheelite by FTIR and the wettability change of the usual cleavage plane, and proved that water glass inevitably influenced the flotation of tungsten minerals to a large extent in traditional fatty acid flotation process. A new collector, lead complexes of benzohydroxamic acid, was found to be selective for the separation of scheelite and calcium minerals with little water glass. Hence a novel flotation process was developed for the recovery of tungsten minerals in Shizhuyuan Mine in China. Normal temperature flotation of tungsten minerals was developed to instead of the classical “Petrov's process” for scheelite-calcite-fluorite type ores. Compared with the traditional process, the recovery was improved by almost 10% and the grade of scheelite concentrate was above 55%. The disappearance or decreasing of water glass contributed to improving the recovery of tungsten and the circulation of water and reagents.