New asymmetrical pyridine- and isoquinoline-functionalized bis(pyrazolate) Pt(ii) metallomesogens have been engineered and designed to exhibit multifunctional properties in terms of mesomorphism, photoluminescence and ionic conductivity near room temperature. The molecules are self-assembled in hexagonal columnar mesophases via PtPt interactions, which generates a strong orange-red emission as a result of the formation of triplet metal-metal-to-ligand charge-transfer (3MMLCT) excited states. Concomitantly, the hexagonal columnar mesophases open continuous nanochannels that have been used for proton conduction over a wide range of temperatures. It is also noteworthy that the luminescence typically decreases with temperature, whereas the ionic conductivity increases to values of the order of 10−5 Ω−1 cm−1 at ca. 300 °C in the mesophase.