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Superconducting properties of two bismuthide intermetallic compounds, RbBi2and CsBi2, were studied by means of experimental measurements and ab initiocalculations. We show that in both compounds, the superconductivity emerges from the pyrochlore Bi lattice and its formation is heavily influenced by relativistic effects. Based on our analysis of the effect of spin–orbit coupling on the electron–phonon coupling, we suggest a possible criterion for finding new superconducting materials by looking for structures featuring relativistically stabilized hypervalent networks of heavy p-block elements.