The excitonic radiative recombination of intercalated Cl2 molecules for two different polytypes 2H-MoS2 and 3R-MoS2 layered crystals are presented. The structure of the excitonic emission is unique and provides a robust experimental signature of crystal polytype investigated. This result is confirmed by X-ray diffraction analysis and DFT electronic band structure calculations. Thus, the bound exciton emission provides a nondestructive fingerprint for the reliable identification of the polytype of MoS2 layered crystals.