As-doped ZnO (ZnO:As) films have been characterized. ZnO:As films show p-type characteristics determined by Hall-effect and photoluminescence (PL) measurements. The hole concentration can be increased up to the mid-1017-cm−3 range. The thermal binding energy of the As acceptor (EAth-b) is 120±10 meV, as derived from temperature-dependent Hall-effect measurements. The PL spectra reveal two different acceptor levels (EAopt-b), located at 115 and 164 meV, respectively, above the maximum of the ZnO valence band, and also show the binding energy of the exciton to the As-acceptor (EAXb) is about 12 meV. The values of the ratio EAXb/(EAth-b or EAopt-b) are located in the range from 0.07 to 0.11.