The supramolecular chemistry of the third generation poly(propyleneimine) dendrimers (1) having adamantylurea end groups was investigated using multidimensional NMR on a 750 MHz spectrometer. A stable complex (3) is formed when 1 is combined with cyanobiphenyl guest molecules (2) having glycinylurea type end groups. Proton connectivities were obtained from 2D H-1-H-1 TOCSY experiment. The C-13 and H-1 resonances were correlated from the 2D H-1-C-13 gHSQC experiment. Spatial proximity of the host-guest molecules was determined from a 2D H-1-H-1 NOESY experiment. Evidence of the specific binding interactions responsible for the stable complex of 1 with 2 was obtained from H-1-H-1 interactions determined from the NOESY spectrum.