In this work, the hierarchal arrangement of peptide nanowires was achieved via the spontaneous crystallization of peptide molecules. Peptide molecules, which are structural motifs associated with Alzheimer's disease, assembled into one-dimensional nanowires and spontaneously formed two-dimensional peptide spherulites during crystallization of the peptide melt. The assembly behavior of the peptides could be directed by physically confining the soft mold. Furthermore, a hybrid assembly of small functional molecules, such as photoluminescent Alq3, was also achieved. Our approach offers a simple method for achieving spontaneous long-range crystalline order of building blocks approaching macroscopic dimensions and also a facile hybridization strategy to conjugate biomolecules and functional small molecules.