Bioethanol is a promising candidate for acetaldehyde production. In this study, we controllably unzipped multi-walled carbon nanotubes into open-edged nanotube/nanoribbon hybrids via a nano-cutting strategy for metal-free oxidative dehydrogenation of ethanol to acetaldehyde and unravelled the catalytic role of edge defects in the reaction. The edge-rich structure of the 1D-nanotube/2D-nanoribbon hybrid can accelerate the catalytic reaction more efficiently than pristine carbon sample. Moreover, edges can further accommodate nitrogen defects to preferentially form edge-doped nitrogen. Through engineering the concentration and speciation of defects, the structure-performance relationship between the defective structure and ethanol conversion rate is intensively investigated. Theoretical calculations unveil that the nitrogen doped at edge sites other than in basal planes can effectively facilitate O2 dissociation and formation of oxygen-containing active centers. Temperature-programmed ethanol desorption and kinetic measurements further supplement the catalytic interplay of edge and nitrogen defects on ethanol adsorption and reaction kinetics. The synergistic edge and nitrogen defects of the engineered hybrid produced a steady ethanol conversion of 47.9% and acetaldehyde selectivity of 90.2% at the gas hourly space velocity of 48,000 mL gcat-1h−1 on stream of 48 h. This work offers more insights to intrinsic properties and mechanism of enriched defective structures for development of effective carbocatalysts in catalytic applications.