ZnO/carbon-black heterostructures were synthesized using a sol–gel method and crystallized by annealing at 500 °C under 2 × 10−2Torr for 10 min. The crystal structures and binding vibration modes were determined by XRD, HRTEM, and Raman spectrometry. Their surface morphologies were observed by FESEM. The Moiré pattern that is observed in the HRTEM images confirms that the carbon-black nanoparticles were covered by the ZnO crystals. Measurements of optical absorptance revealed that the optical band gap of the ZnO/carbon-black heterostructures increased from 2.33 to 2.98 eV as the carbon-black nanoparticle content increases from 0 to 8.33 × 10−3mol owing to the Burstein–Moss effect. The photoluminescence intensities at the near-band edge and of the violet, and blue light were increased by factors about 68.3, 62.8, and 56.8, respectively, when the carbon-black contents is of the 2.03 × 10−3mol. This work reveals that the proper carbon-black nanoparticle content involved increases the PL intensities of the ZnO crystals in the short wavelength regime, supporting their potential application in the light-emitting devices.