Maletoyvayamite, Au3Se4Te6, is a new mineral discovered in a heavy-mineral concentrate from the Gaching occurrence of the Maletoyvayam deposit, Kamchatka, Russia (60°19′51.87″N, 164°46′25.65″E). It forms anhedral grains (10 to 50 μm in size) and is found in intergrowths with native gold (Au–Ag), Au tellurides (calaverite), unnamed phases (AuSe, Au2TeSe and Au oxide), native tellurium, sulfosalts (tennantite, tetrahedrite, goldfieldite and watanabeite) and supergene tripuhyite. Maletoyvayamite has a good cleavage on {010} and {001}. In plane-polarised light, maletoyvayamite is grey, has strong bireflectance (grey to bluish grey), and strong anisotropy; it exhibits no internal reflections. Reflectance values for maletoyvayamite in air (Rmin,Rmax in %) are: 38.9, 39.1 at 470 nm; 39.3, 39.5 at 546 nm; 39.3, 39.6 at 589 nm; and 39.4, 39.7 at 650 nm. Sixteen electron-microprobe analyses of maletoyvayamite gave an average composition: Au 34.46, Se 16.76, Te 47.23 and S 0.84, total 99.29 wt.%, corresponding to the formula Au2.90(Se3.52S0.44)Σ3.96Te6.14 based on 13 atoms; the average of eleven analyses on synthetic analogue is: Au 34.20, Se 19.68 and Te 45.42, total 99.30 wt.%, corresponding to Au2.90Se4.16Te5.94. The calculated density is 7.98 g/cm3. The mineral is triclinic, space group P1, with a = 8.901(2), b = 9.0451(14), c = 9.265(4) Å, α = 97.66(3), β = 106.70(2), γ = 101.399(14)°, V = 685.9(4) Å3 and Z = 2. The crystal structure of maletoyvayamite represents a unique structure type resembling a molecular structure. There are cube-like [Au6Se8Te12] clusters linked via van der Waals interactions. The structural identity of maletoyvayamite with the synthetic Au3Se4Te6 was confirmed by powder X-ray diffraction and Raman spectroscopy.