At Arvogno, Vigezzo valley in the Central Alps, Italy, pegmatite dikes are unique in the scenario of a tertiary alpine pegmatite field because they show marked geochemical and mineralogical niobium–yttrium–fluorine features. These pegmatites contain AB2O6 aeschynite group minerals and ABX2O8 euxenite group minerals as typical accessory minerals including aeschynite-(Y), polycrase-(Y), and samarskite-(Y). They are associated with additional typical minerals such as fluorite, Y-dominant silicates, and xenotime-(Y). The Y–Nb–Ti–Ta AB2O6 and ABX2O8 oxides at the Arvogno pegmatites did not exhibit any textural and compositional features of oxidation or weathering. They are characterized by low self-radiation-induced structural damage, leading to the acquisition of unit-cell data for aeschynite-(Y), polycrase-(Y), and samarskite-(Y) by single-crystal X-ray diffraction. Aeschynite-(Y) and polycrase-(Y) crystals allowed for both to provide space groups whereas samarskite-(Y) was the first crystal from pegmatites for which cell-data were obtained at room temperature but did not allow for the accurate determination of the space group. According to the chemical compositions defined by Ti-dominant content at the B-site, the cell parameters, respectively, corresponded to polycrase-(Y), aeschynite-(Y), and the monoclinic cell of samarskite-(Y). Emplacement of Alpine pegmatites can be related to the progressive regional metamorphic rejuvenation from east to west in the Central Alps, considering the progressive cooling of the thermal Lepontine Barrovian metamorphic dome. Previous studies considered magmatic pulses that led to emplace the pegmatite field in the Central Alps. As an example, the pegmatites that intruded the Bergell massif were aged at 28–25 millions of years or younger, around 20–22 m.y.