The new alluaudite-group mineral khrenovite with the ideal, end-member formula Na3Fe3+2(AsO4)3 was found in the Arsenatnaya fumarole, Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with aphthitalite-group sulfates, badalovite, calciojohillerite, nickenichite, johillerite, tilasite, svabite, achyrophanite, ozerovaite, pansnerite, arsenatrotitanite, anhydrite, sanidine, hematite, cassiterite, rutile and pseudobrookite. Khrenovite occurs as coarse prismatic crystals up to 0.2 × 0.3 × 0.8 mm and their clusters up to 1 mm across. It is transparent, honey-coloured, red-, orange- or yellow-brown, with vitreous lustre. Khrenovite is brittle, cleavage was not observed. Dcalc is 4.257 g cm–3. Khrenovite is optically biaxial (+), α = 1.825(7), β = 1.834(7), γ = 1.845(7) and 2Vmeas. = 80(10)°. The chemical composition (wt.%, electron-microprobe) is: Na2O 11.47, K2O 1.23, CaO 0.18, MgO 0.01, MnO 4.10, CuO 4.27, ZnO 1.99, Al2O3 0.17, Fe2O3 21.12, SiO2 0.08, P2O5 0.01, V2O5 0.10, As2O5 56.03, SO3 0.02, total 100.78. The empirical formula calculated on the basis of 12 O apfu is (Na2.26K0.16Ca0.02Mn0.35Cu0.33Zn0.15Al0.02Fe3+1.62)Σ4.91(As2.98Si0.01V0.01)Σ3.00O12. Khrenovite is monoclinic, C2/c, a = 12.2394(7), b = 12.7967(5), c = 6.6589(4) Å, β = 112.953(7)°, V = 960.37(10) Å3 and Z = 4. The crystal structure was solved from single-crystal X-ray diffraction data with R1 = 0.0287. Khrenovite is isostructural with other alluaudite-group minerals. Its structural formula simplified to the species-defining constituents is A(1)NaA(2)’NaM(1)NaM(2)Fe3+2(TAsO4)3. The mineral is named in honour of the Russian volcanologist and geologist Anatoly Petrovich Khrenov (1946–2016).