The syntheses of 1,3-bis(alpha-picolyloxy)-p-tert-butylcalix[4]arene crown-6 and 1,1'-binaphthalene2,2'-diyl crown-6 title conformers have been achieved by two complementary synthetic strategies. The structure and conformation of all new compounds have been firmly established by NMR spectroscopy, and proven by X-ray analysis. The alkali metal ion binding selectivities of the two series of calixarenes have been evaluated in competitive complexation experiments by electrospray ionization mass spectrometry.