The difference in the morphology and crystallization aspects of hydrogen-bond-mediated self-assembling systems with single and double hydrogen-bonding motifs is studied here with carbamates as an example. These carbamates have alkyl side chains of various lengths, from C-4 to C-18. The biscarbamates with double hydrogen-bonding sites and symmetric substitution of alkyl segments show a significantly different morphological behavior as compared to the N-octadecyl carbamate alkyl esters (ref 5, referred to as simple carbamates henceforth) with a single hydrogen-bond motif and asymmetric substitution of alkyl side chains. In contrast to the simple carbamates in which no significant difference was found in the spherulite size from C-4 to C-12, with the biscarbamates we find that the spherulitic size, rate of growth of spherulites, and rate of crystallization show a maximum with an alkyl chain length of C-8. This is rationalized in terms of the relative contributions of the hydrogen-bond and van der Waals interaction energies. Oriented X-ray diffraction patterns from the fibrils of the spherulites lead to a model for the growth patterns of the hydrogen-bond planes and the molecular orientation in the spherulites.