Four monomeric building blocks equipped with one crown ether and one secondary ammonium ion are synthesized and studied with respect to their ability to form daisy chain dimers. Two crown ethers with different cavity sizes – i.e. [21]crown-7 and [24]crown-8 – and two ammonium ions substituted with either a thin alkyl group or a more bulky benzyl group are used as the binding motifs. Self-sorting behaviour can be expected as the [21]crown-7/alkyl ammonium and [24]crown-8/benzyl ammonium binding motifs are orthogonal. Three homodimers are characterized by NMR, X-ray crystallo-graphy and ESI mass spectrometry. They are recognizable by the presence of signals for diastereotopic protons in the 1H NMR spectra. The formation of hetero-[c2]daisy chain dimers can be monitored by NMR spectroscopy and ESI mass spectrometry and show the expected self-sorting behaviour.