Formation of compounds RbPbI3 and Rb4PbI6 in the RbI–PbI2 system is revealed, and their absorption spectra are investigated in an energy interval of 2–6 eV and at temperatures from 90 to 500 K. It is established that the low-frequency exciton excitations are localized in PbI64− structural elements of the crystal lattice, they are classified as excitons of intermediate coupling and are of a three-dimensional character in RbPbI3 and a quasi-two-dimensional one in Rb4PbI6.

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