Rinkite, ideally Na2Ca4REETi(Si2O7)2OF3, is a common mineral in alkaline and peralkaline rocks. The crystal structures of five rinkite crystals from three alkaline massifs: Ilimaussaq, Greenland; Khibiny, Kola Peninsula, Russia and Mont Saint-Hilaire, Canada, have been refined as two components related by the TWIN matrix (−1 0 0, 0 −1 0, 1 0 1) (Mo-Kα radiation). The crystals, a = 7.4132–7.4414, b = 5.6595–5.6816, c = 18.8181–18.9431 Å, β = 101.353–101.424(2)°, V = 776.1–786.7 Å3, space group P21/c, Z = 2, Dcalc = 3.376–3.502 g cm−3, were analysed using an electron microprobe subsequent to collection of the X-ray intensity data. Transmission electron microscopy confirmed the presence of pseudomerohedral twinning in rinkite crystals. The crystal structure of rinkite is a framework of TS (titanium silicate) blocks. The TS block consists of HOH sheets (H-heteropolyhedral, O-octahedral). The TS block in rinkite exhibits linkage and stereochemistry typical for Group I (Ti = 1 a.p.f.u.) of Ti disilicate minerals: two H sheets connect to the O sheet such that two (Si2O7) groups link to the trans edges of a Na polyhedron of the O sheet. The crystal chemistry of rinkite and nacareniobsite-(Ce) is discussed.