This study reports the synthesis of covalent, inherently chiral open-[60]fullerene dimers with radial π-conjugation. The researchers used open-[60]fullerene molecules as precursors and employed a phosphine-mediated sequential deoxygenation strategy to achieve the desired chiral conjugates. The resulting dimers exhibit strong electronic communication, intense absorption behavior, and chiroptical activity with a dissymmetry factor of 0.21 at 674 nm, which is among the highest recorded for chiral organic molecules. The crystallographic analysis confirmed the double-caged structure of the dimers, with the two [60]fullerene cages connected by a covalent bond. The dimers also display heterochiral recognition, enabling the arrangement of four carbon cages in a tetrahedral manner in both solution and solid state. The study highlights the potential of these chiral nanocarbon assemblies for applications in chiroptoelectronic devices and the design of non-naturally occurring inter-[60]fullerene allotropes. The synthesis involved three strategies: Wittig reaction, aldol condensation, and consecutive deoxygenation, with the latter being most effective. The dimers were characterized using various techniques, including NMR, X-ray crystallography, and UV-vis-NIR spectroscopy. The results demonstrate the successful synthesis of chiral open-[60]fullerene conjugates with unique electronic and chiroptical properties.This study reports the synthesis of covalent, inherently chiral open-[60]fullerene dimers with radial π-conjugation. The researchers used open-[60]fullerene molecules as precursors and employed a phosphine-mediated sequential deoxygenation strategy to achieve the desired chiral conjugates. The resulting dimers exhibit strong electronic communication, intense absorption behavior, and chiroptical activity with a dissymmetry factor of 0.21 at 674 nm, which is among the highest recorded for chiral organic molecules. The crystallographic analysis confirmed the double-caged structure of the dimers, with the two [60]fullerene cages connected by a covalent bond. The dimers also display heterochiral recognition, enabling the arrangement of four carbon cages in a tetrahedral manner in both solution and solid state. The study highlights the potential of these chiral nanocarbon assemblies for applications in chiroptoelectronic devices and the design of non-naturally occurring inter-[60]fullerene allotropes. The synthesis involved three strategies: Wittig reaction, aldol condensation, and consecutive deoxygenation, with the latter being most effective. The dimers were characterized using various techniques, including NMR, X-ray crystallography, and UV-vis-NIR spectroscopy. The results demonstrate the successful synthesis of chiral open-[60]fullerene conjugates with unique electronic and chiroptical properties.