Kalyuzhnyite-(Ce), ideally NaKCaSrCeTi(Si8O21)OF(H2O)3, is a new mineral from the Darai-Pioz alkaline massif, Tien-Shan mountains, Tajikistan. It occurs as equant grains up to 0.05 × 0.07 mm in a quartz–pectolite aggregate in a silexite-like peralkaline pegmatite. Associated minerals are quartz, fluorite, pectolite, baratovite, aegirine, leucosphenite, neptunite, reedmergnerite, orlovite, sokolovaite, mendeleevite-(Ce), odigitriaite, pekovite, zeravshanite, kirchhoffite and garmite. The mineral is colourless with a vitreous lustre and a white streak, and Dcalc. is 3.120 g/cm3. Kalyuzhnyite-(Ce) is monoclinic, P2/c, a = 18.647(4), b = 11.214(2), c = 14.642(3) Å, β = 129.55(3)° and V = 2360.9(11) Å3. The chemical composition of kalyuzhnyite-(Ce) is Nb2O5 0.53, TiO2 0.16, SiO2 43.85, Er2O3 0.13, Ho2O3 0.10, Gd2O3 0.09, Sm2O3 0.47, Nd2O3 6.22, Pr2O3 1.21, Ce2O3 6.34, La2O3 0.82, PbO 4.90, BaO 0.85, SrO 11.39, CaO 1.86, Cs2O 3.80, K2O 1.59, Na2O 2.99, H2O 5.24, F 1.55, O = F –0.65, total 100.31 wt.%. The empirical formula calculated on 26.11 (O + F) apfu is Na1.07K0.37Cs0.30Sr1.21Ca0.37Pb0.24Ba0.06(Ce0.43Nd0.41Pr0.08La0.06Sm0.03Gd0.01Er0.01Ho0.01)Σ1.04(Ti0.97Nb0.04)Σ1.01Si8.06O25.21F0.90H6.42, Z = 4. The simplified formula is (Na,□)(K,Сs)(Ca,Pb,Sr,Na)SrLn3+Ti(Si8O21)OF(H2O)3, where Ce is the dominant lanthanoid. The crystal structure was solved by direct methods and refined to an R1 index of 2.74%. In kalyuzhnyite-(Ce), the main structural units are a heteropolyhedral Na–Sr–Ce–Ti sheet, ideally [NaSrCeTiOF]7+, and a double (Si8O21)10– sheet parallel to (010). In the Si–O sheet, the Si tetrahedra form ten-membered rings. This is the first occurrence of such a double Si–O sheet in a mineral. The two sheets connect via common vertices of Na-, Sr-, Ce- and Ti-polyhedra and SiO4 tetrahedra to form a framework. The interstitial cations and H2O groups, ideally [(CaK)(H2O)3]3+, occur within the Si–O sheet. The mineral is named in honour of Vasily Avksentievich Kalyuzhny (1899–1993) in recognition of his contributions to the geology of ore deposits of Komi Republic (USSR) and the mineralogy of granitic pegmatites (Tajikistan).