Piperidine and 1,1,1-3,3,3 hexafluoro-2-propanol (HFIP) have been co-crystallized and X-ray crystal structure has been explored. Single-crystal X-ray analysis displays the existence of hydrogen bonding aggregates through dimers 1 of the complex (one piperidine/two HFIP) where the heteroatoms form a six-center ring. In this cluster 1, each heteroatom (N, O) is multiple H-bond donor and acceptor. Surprisingly the strongest H-bond of the network is where HFIP acts as an acceptor from the amine. In this complex HFIP adopts a conformation different from that of HFIP aggregates. The supramolecular architecture is also based on discrimination between polar and hydrophobic parts that allows the alignment of molecules and the formation of parallel channels. NMR experiments show that strong interactions between piperidine and HFIP are maintained in solution.