Crystal structures along the join beryl–pezzottaite have been refined and their compositions determined by electron-microprobe analysis. All crystals show sharp uniform diffraction spots but are microscale mixtures of more than one structure. Three distinct phases were identified with different diffraction characteristics: (1) hexagonal (P6/mcc) Cs-rich beryl; (2) hexagonal–rhombohedral ($R\overline 3 c$) twinned pezzottaite; (3) incommensurate phases with cell dimensions resembling those of beryl with a doubled c-dimension and l indices deviating from integer values by ±0.05–0.10. Beryl (P6/mcc) structures refined to R1 indices from 2.36 to 2.91% and pezzottaite structures refined to R1 indices from 3.31 to 5.83%. In pezzottaite, the Cs1 and Cs2 sites are each occupied by Cs+, Rb+ and (H2O) with Cs+ showing a preference for Cs1; and the Na1 and Na2 sites are occupied by Na+ and Ca2+. Na+ bonds to one (H2O) group and (H2O) bonds to one Na+. The ordering of (Cs+ + Rb+) and (Na+ + Ca2+) in pezzottaite is driven by the incident bond-valence requirements of the anions coordinating the (LiO4) tetrahedron. The valence-sum rule is maintained through the (Cs+ + Rb+) + Li+ → □ + Be2+ variation in beryl by cooperative relaxation of bonds at the Si and Be tetrahedra, and in pezzottaite by cooperative relaxation of bonds at the Si, Al and Li tetrahedra. The valence-sum rule mandates that Na+ must bond to one channel (type-II) (H2O) group which, when combined with the constraint of electroneutrality, requires that compositions along the beryl–pezzottaite join must lie below the line (Cs+ + Rb+) + 2(Na+ + Ca2+) = 1 – 2Ca2+ apfu. The occurrence of an incommensurate phase at intermediate compositions is due to the interaction of the species in adjacent columns of the P6/mcc beryl structure.