The ideal bone scaffold harnesses the body's ability to regenerate bone in critical size defects. A potential strategy to design the ideal bone scaffold is to mimic the natural structure of bone at the molecular level. The orientation and spatial distribution of nanocrystals in the organic matrix are two important and distinctive structural characteristics associated with natural bone. There has yet to be a synthetic system or scaffold that is able to control both the spatial distribution and orientation of the hydroxyapatite crystalline structure. To mimic the unique hybrid structure of natural bone using synthetic materials, there have been a number of reported approaches to control the mineral nanocrystal orientation on synthetic scaffolds. However, the spatial distribution of minerals is challenging to reproduce in a biomimetic manner. Herein we report using block copolymer-decorated polymer nanofibers to achieve biomineralized fibrils with precise control of both mineral crystal orientation and spatial distribution. We show that the crystallization of poly(caprolactone)-b-poly(acrylic acid) block copolymer on poly(caprolactone) nanofibers resulted in a unique shish kebab structure that significantly enhances the mechanical properties of the nanofibers, and is cytocompatible to L-929 mouse fibroblast cells. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 1786-1798, 2017.