Abstract With the view to examine the role of d*‐d transitions of Ni in energy up conversion and in other photonic devices, photoluminescence spectral investigation near infrared region (10000 cm –1 to 12000 cm –1 ) was carried out at 10 K and 300 K in diluted magnetic semiconductor, Zn 1–x Ni x S. The samples were specially grown for this investigation. Some new emission lines along with a broad emission band are observed. Their origin is discussed on the basis of the transition from the excited T 2 ( 1 D) state to the ground state A 1 ( 3 F). The role of a splitted valence band structure and the presence of Ni + state in photoluminescence is also discussed. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)