Deep-level transient spectroscopy (DLTS) has been used to measure the concentration and energy position of deep electronic states in CuInS2. Flat TiO2∣CuInS2 heterojunctions as well as TiO2-CuInS2 nanocomposites have been investigated. Subband-gap electronic states in CuInS2 films are mostly due to antisite point defects and vacancies. Substitution of indium with copper, CuInII, leads to an acceptor state 0.15 eV above the valence band, while copper vacancies, VCuI, are acceptor states at 0.1 eV. Furthermore, indium on a copper position, InCu″, yields a donor state at 0.07 eV below the conduction band, while sulphur vacancies are donor states at 0.0 = eV. With DLTS, these states are indeed found. For flat configurations, VCuI are the dominant acceptors with a concentration of 1.83×1017 cm−3. In contrast for nanocomposites CuInII are the dominant acceptors having a concentration of 6.7×1017 cm−3. We conclude that the concentration of antisite defects in nanocomposite CuInS2 is significantly higher than that in flat films of CuInS2.