Thunderbayite (IMA2020–042), ideally TlAg3Au3Sb7S6, is a new mineral from the Hemlo gold deposit, Marathon, Ontario, Canada. It occurs as very rare anhedral rims up to 70 μm across in contact with aurostibite and associated spatially with stibarsen, biagioniite and native gold in a calcite matrix. Thunderbayite is opaque with a metallic lustre and shows a black streak. In reflected light, thunderbayite is weakly bireflectant and faintly pleochroic from grey–blue to slightly greenish grey–blue. Under crossed polars, it is weakly anisotropic with bluish to light-blue rotation tints. Internal reflections are absent. Reflectance percentages for the four Commission on Ore Mineralogy wavelengths (Rmin, Rmax) are: 37.9, 38.4 (471.1 nm); 35.3, 36.0 (548.3 nm); 33.9, 34.4 (586.6 nm); and 32.0, 32.5 (652.3 nm), respectively. A mean of five electron-microprobe analyses gave Ag 14.91(16), Au 27.40(22), Tl 9.37(9), Sb 39.80(34) and S 8.61(7), for a total of 100.09 wt.%, corresponding, on the basis of a total of 20 atoms, to Tl1.00Ag3.01Au3.03Sb7.12S5.84. Thunderbayite is triclinic, space group P1, with a = 8.0882(5), b = 7.8492(5), c = 20.078(1) Å, α = 92.518(5), β = 93.739(5), γ = 90.028(6)°, V = 1270.73(9) Å3 and Z = 2. The five strongest powder-diffraction lines [d in Å (I/I0) (hkl)] are: 4.04 (100) (200); 3.92 (80) (020); 2.815 (50) (220/$\bar{2}$20); 2.566 (45) ($\bar{1}$17); and 2.727 (40) (0$\bar{1}$7). The crystal structure [R1 = 0.0220 for 5521 reflections with I > 2σ(I)] can be considered as a strongly deformed pyrite-type structure with several metal–metal bonds. Thunderbayite shows close similarities with criddleite, TlAg2Au3Sb10S10, from an optical, chemical and structural point of view. The new mineral is named for the Thunder Bay district, Ontario, in which the Hemlo gold deposit is located.