Supramolecular nanocatalysts were designed for asymmetric reactions through the self-assembly process of a bio-organometallic molecule, ferrocene-L-prolinamide (Fc-CO-NH-P). Fc-CO-NH-P could self-assemble into versatile nanostructures in water, including nanospheres, nanosheets, nanoflowers, and pieces. In particular, the self-assembled nanoflowers exhibited a superior specific surface area, high stability, and delicate three-dimensional (3D) chiral catalytic active sites. The nanoflowers could serve as heterogeneous catalysts with an excellent catalytic performance toward direct aldol reactions in aqueous solution, achieving both high yield (>99%) and stereoselectivity (anti/syn = 97:3, ee% >99%). This study proposed a significant strategy to fabricate supramolecular chiral catalysts, serving as a favorable template for designing new asymmetric catalysts.