Baeyer–Villiger (BV) oxidation is a fundamental organic reaction, whereas the hetero-BV oxidation is uncharted. Herein, a tellura-BV oxidation is discovered. By oxidizing a tellurophene-embedded and electron-rich polycycle (1) with mCPBA or Oxone, an oxygen atom is inserted into the Te–C bond of the tellurophene to form tellurinate lactone mono-2. This reaction proceeds as follows: (i) 1 is oxidized to the tellurophene Te-oxide form (IM-1); (ii) IM-1 undergoes tellura-BV oxidation to give mono-2. Moreover, the hybrid trichalcogenasumanenes 7 and 8 are, respectively, converted to tellurinate lactones mono-9 and mono-10 under the same conditions, indicating that tellura-BV oxidation shows high chemoselectivity. Due to the strong secondary bonding interactions between the TeO groups on tellurinate lactones, mono-2, mono-9, and mono-10 are dimerized to form U-shaped polycycles 2, 9, and 10, respectively. Notably, mono-2, mono-9, mono-10, and their dimers show chirality. This work enables one-step transformation of tellurophene into tellurinate lactone and construction of intricate polycycles.