Two enantiomers with helical carbon frameworks (M-HCFa and P-HCFa) and their conformational isomers (M-HCFb and P-HCFb) have been synthesized and characterized. The single-crystal analysis revealed the novel structures in which three propeller blades spiro-fused on two central benzene rings. The optical properties were further investigated, and stable bipolar electrochemiluminescence emissions were discovered for the first time existing in helical carbon frameworks, which provide new insights into the future development of high-performance molecular luminescent devices.