Elemental Tellurium (Te) is an important p‐type semiconductor with wide practical applications. It is currently of great interest as a chiral crystal with broken inversion and mirror symmetries, and its topological nature is under active discussion. Here the Shubnikov–de Haas (SdH) oscillations with a nontrivial π Berry phase and the quantum linear magnetoresistance (MR) in as‐synthesized high‐mobility Te single crystals are reported. The vapor transport grown Te shows a hollow hexagonal prism structure with tunable carrier density and high mobility of about 1000 cm2 V−1 s−1 at low temperature. For concentration p > 1017 cm−3, the conspicuous SdH oscillations map out the dumbbell‐shaped Fermi surface and the long‐standing peculiar amplitude change with varying magnetic field orientation is explained by careful quantitative analyses. Pulsed magnetic field measurements up to 57 T disclose a quantum linear MR beyond the quantum limit and the Landau fan diagram clearly reveals a topologically nontrivial π Berry phase. This work paves way for the synthesis of high‐mobility Te structures and sheds light onto the intrinsic nontrivial topology of the attractive elemental substance.