The orientation and spatial distribution of nanocrystals in the organic matrix are two distinctive structural characteristics associated with natural bone. Synthetic soft materials have been used to successfully control the orientation of mineral crystals. The spatial distribution of minerals in a synthetic scaffold, however, has yet to be reproduced 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. Exquisite nanoscale structural control in biomimetic hybrid materials has been demonstrated. http://pubs.acs.org/doi/pdf/10.1021/nn403742f