The tungsten distribution in rocks of the Kukulbei Complex in eastern Transbaikal region results in a high potential of rare-metal peraluminous granites (RPG) for W mineralization and displays a different behavior of W in Li–F and “standard” RPG. These subtypes differ in the behavior of W in melt, spatial localization of mineralization, and the timing of wolframite crystallization relative to the age of the parental granitic rocks. The significant of W concentration is assumed to be due to fractionation of the Li–F melt; however, wolframite mineralization in Li–F enriched granite is not typical in nature. The results of experiments and our calculations of W solubility in granitic melt show that wolframite hardly ever crystallizes directly from melt; it likely migrates in the fluid phase and is then removes from the magma chamber to the host rocks, where secondary concentration takes place in exocontact greisens and quartz–cassiterite–wolframite veins. At the same time, the isotopic age of accessory wolframite (139.5 ± 2.1 Ma) within the Orlovka massif of Li–F granite is close to the formation age of the massif (140.6 ± 2.9 Ma). A different W behavior is recorded in the RPG subtype with a low lithium and fluorine concentration, exemplified by the Spokoininsky massif. There is no significant W gain in the melt. All varieties of wolframite mineralization in the Spokoininsky massif are derived from greisens, veins, and pegmatoids yielding the same crystallization ages (139.5 ± 1.1 Ma), which are 0.9–1.8 Ma later (taking into account the mean-square weighted deviation) than the Spokoininsky granite formation (144.5 ± 1.4 Ma). Perhaps this period corresponds to the time of transition from the magmatic stage to hydrothermal alteration. Comparison of the isotope characteristics (Rb–Sr and Sm–Nd isotope systems) of rocks and the associated ore minerals (wolframite, cassiterite) from all examined deposits shows a depletion in ε_Nd values for ore minerals relative to the rock and the opposite behavior for the intial Sr isotope ratios. This may indicate the specific nature of ore matter, where the effect of the juvenile component is definitely expressed. Our geochronological results show that tantalum and tungsten mineralization took place within a narrow age interval, almost synchronously with the crystallization of associated granites. The coeval development of peraluminous magmatism enriched in lithophile rare elements and volatiles with ore complexes located in different structural settings and separated by a considerable distance from each other (up to 500 km) suggests a regional and deep-seated magma source. Rifting and increased thermal flux from the mantle, manifestations of which have been recorded during this period in the territory, may be a deep-seated process.