Two samples of thin films, assembled by CuCl nanoclusters, have been prepared by the gas evaporation technique. The CuCl nanoclusters were deposited on monocrystalline silicon and quartz substrates and then coated with a layer of NaCl to prevent oxidation of the CuCl nanoclusters. From transmission electron microscope and selected area diffraction, it is clear that the two samples consist of CuCl nanocrystals and Cu aggregates and the mean diameters are about 3 nm and 6 nm. From the absorption and photoluminescence (PL) spectra of the two samples carried out at ~300 K, we found that the peaks of exciton absorption do not show up and luminescence peaks shift to lower energies, possibly due to the strong coupling between exciton and phonon. At 77 K, the PL peaks of excitons broadened by exciton–phonon coupling have been observed, in approximate agreement with the values calculated by the quantum confinement model. The broad peaks of emission from trapped states or bands have also been observed at 77 K. In addition, the interaction between exciton and phonon is stronger in the sample with mean diameter about 3 nm according to a larger broadening and redshift of the PL peak from excitons, in qualitative agreement with theoretical prediction.