Hematoxylin has a V-shaped chiral geometry, but its potential in chiroptical self-assembled materials is underdeveloped. Herein, three novel V-shaped chiral hematoxylin derivatives were synthesized, and they showed extended skeletons as well as photophysical and chiroptical behaviors. Moreover, their host-guest interactions with C60 were investigated. Our findings could aid in the design and synthesis of novel chiral host molecules from natural products.