AbstractBimacrocyclic concave pyridinebissulfonamides2and concave 1,10‐phenanthrolinebissulfonamides4have been synthesized by bridging macrocyclic pyridinediamines12or 1,10‐phenanthrolinediamines16with alkylenebis(sulfonyl chloride)s14. In contrast to concave pyridine‐ and 1,10‐phenanthrolinebislactams1and3, the new compounds2and4exhibit simpler1H‐NMR spectra and sharper melting points due to the absence of amide conformers; in comparison to1, the basicities of2are decreased by a factor of ca. 100. By introduction of donor substituents into the 4‐position of the pyridine ring the basicity loss can be easily compensated. The 4‐diethylamino substituent increases the basicity of the concave pyridines1and2as expected (ca. + 4 pKunits). Since no deviations from the expected basicity and reactivity for the amino‐substituted concave pyridines1and2have been found, also in these sterically hindered pyridines, the pyridine nitrogen atom is the centre of basicity and reactivity. – The synthesis of new building blocks is described, i.e. 4‐diethylamino‐2,6‐pyridinedicarbaldehyde (9c), the polyether‐based bis(sulfonyl chloride)14b, the monomacrocyclic diamines12e–hwith a pentaethyleneglycol chain or a