The first slipped pseudo-quadruple-decker complex of phthalocyanines was formed unexpectedly upon treatment of the protonated double-decker (SmH)-H-III(Pc)[PC(alpha-OC4H9)(8)] with NaOH, The supramolecular structure contains two double-decker units linked by two sodium ions by an extremely rare coordination mode of phthalocyanines in which an aza nitrogen atom and two oxygen atoms from neighboring alkoxy substituents form a tridentate ligand.