Chloroform and other volatile organic pollutants have garnered widespread attention from the public and researchers, because of their potential harm to the respiratory system, nervous system, skin, and eyes. However, research on chloroform vapor sensing is still in its early stages, primarily due to the lack of specific recognition motif. Here we report a mesoporous photonic crystal sensor incorporating carbon dots-based nanoreceptor (HMSS@CDs-PCs) for enhanced chloroform sensing. The colloidal PC packed with hollow mesoporous silica spheres provides an interconnected ordered macro-meso-hierarchical porous structure, ideal for rapid gas sensing utilizing the photonic bandgap shift as the readout signal. The as-synthesized CDs with pyridinic-N-oxide functional groups adsorbed in the hollow mesoporous silica spheres are found to not only serve as the chloroform adsorption sites, but also a molecular glue that prevents crack formation in the colloidal PC. The sensitivity of HMSS@CDs-PCs sensor is 0.79 nm ppm−1 and an impressively low limit of detection is 3.22 ppm, which are the best reported values in fast-response chloroform vapor sensor without multi-signal assistance. The positive response time is 7.5 s and the negative response time 9 s. Furthermore, relatively stable sensing can be maintained within a relative humidity of 20%–85%RH and temperature of 25–55 °C. This study demonstrates that HMSS@CDs-PCs sensors have practical application potential in indoor and outdoor chloroform vapor detection.