We present here observations on the growth habits of a crown ether from the melt. Two spherulites A and B are obtained. It is established that spherulite A has bimolecular layered structure and spherulite B has net-like structure. Atomic force microscopy (AFM) is used to observe the surface morphology X-ray diffraction and IR spectroscopy are used to analyze crystal structure and hydrogen bonding formation. This is the first time to find the molecular self-organization of bimolecular-layered structure and the net-like structure when crystals grow from melt.