The paper presents the first data on the crystal chemistry of the cation-exchanged forms of layered titanosilicates belonging to the epistolite group. It was found that these heterophyllosilicates have high exchange capacity and selectivity for cations of chalcophile elements (Ag, Cu and Zn) and could be considered as potentially novel raw materials or, more likely, as possible prototypes of cation-selective synthetic microporous materials. The crystal structures of Ag- and Cu-exchanged forms of lomonosovite and Ag-exchanged form of murmanite were studied by single-crystal X-ray diffraction. The topology of the main structural unit, the HOH block, remains unchanged in cation-exchanged forms as compared to the initial lomonosovite Na4Ti4(Si2O7)2O4 · 2Na3PO4 (P-1) and murmanite Na4Ti4(Si2O7)2O4 · 4H2O (P-1). In Ag-exchanged murmanite, Ag cations occupy two crystal-lographically non-equivalent positions: one in the heteropolyhedral (H) sheet and another one in the octahedral (O) sheet corresponding to the positions of Na in initial murmanite. The crystal structure of the Ag-exchanged form of lomonosovite is characterized by an increased unit-cell parameter c and doubled parameter b as compared to initial lomonosovite. Ten large-cation sites statistically occupied by Ag and Na correspond to the Na sites in the initial lomonosovite: six in the interlayer space, two in the H sheet and two in the O sheet. Silver significantly replaces Na in sites in the interlayer space and in the O sheet, whereas sites in the H sheet are less affected by the ion exchange. Unit-cell parameter c of the Cu-exchanged form of lomonosovite decreases by 3.58 % as compared to the initial lomonosovite whereas a and b remain almost the same. The Cu cations occupy two crystallographically independent positions. The Cu(1) site, corresponding to the Na(3) site in the initial lomonosovite, is located in the interlayer space. The lowoccupancy Cu(2) site is located on the inversion centre in the O sheet; this site is vacant in the initial lomonosovite. The Cu(2) site is surrounded by six O atoms forming an octahedron distorted due to the Jahn-Teller effect.