Despite considerable challenges and energy costs associated with the perpetual selection of enantiomers and building helix-oriented aggregation in nanostructures, chirality becomes naturally ubiquitous. Spectroscopic investigations aimed at elucidating the selectivity in chiral carbon dots (C–Dots) have revealed the presence of a stereoselective interaction between chiral C–Dots and chiral ligands ( d / l -cysteine). This interaction occurs via different modes of binding in homochiral and heterochiral systems, impacting the charge transfer processes within the composite systems. AC- and DC-bias-driven electrical studies showed how the different chiral ligands control the device activity. The electrical study and transient photocurrent measurements specified that light-induced transient photocurrent is higher in stereoselective homochiral composite systems. These findings on the underlying mechanism of spin selectivity in the C–Dot chiral ligand composite systems are promising to provide a path toward the development of better chiral-sensing electronic devices.