Chiroptical sensing is central to gain fundamental insight into electronic, vibrational and rotational degrees of freedom of chiral molecules, and is a cornerstone for nanomedicine and drug discovery platforms. Current chiral sensing technologies to assess the enantiomeric imbalance of chiral pharmaceutical compounds are sensitive to ml volumes but are time-consuming and cannot be integrated on a chip, thus creating a major bottleneck for drug discovery and nanomedicine. Here, we propose a novel chiroptical sensing approach based on optical rectification in a photonic micro-cavity filled by a drug solution with nl volume. We theoretically demonstrate that, upon optical excitation by intense pulsed laser light, such a nonlinear effect produces a chirally-sensitive nV voltage burst at the electrically-gated micro-cavity boundaries, with sign depending solely on the drug enantiomeric imbalance. Our results shed light on the potential of optical rectification as a robust platform for innovative lab-on-a-chip devices enabling chiral sensing with nl sensitivity.