The carrier spin dynamics in ZnO is investigated by time-resolved optical orientation experiments. We evidence a clear circular polarization of the donor-bound exciton luminescence in both ZnO epilayer and nonintentionally doped bulk ZnO. This allows us to measure the localized hole spin relaxation time. We find h s ϳ 350 ps at T = 1.7 K in the ZnO epilayer. The strong energy and temperature dependences of the photoluminescence polarization dynamics are well explained by the fast free exciton spin relaxation time and the ionization of bound excitons.Wide band gap oxide semiconductor ZnO and its related heterostructures have raised substantial interest in the optoelectronics-oriented research field in the blue/ultraviolet ͑UV͒ range. 1 Besides, with a small spin-orbit coupling and a very large exciton binding energy, ZnO represents a potential candidate for room-temperature ͑RT͒ spintronic applications. However, only few measurements on the carrier spin dynamics in bulk or even nanostructured ZnO have been published to date compared to GaAs-based structures. 2-4 Ghosh et al. 5 have investigated the electron spin properties in n-type ZnO structures and found an electron spin relaxation time varying from 20 ns to 190 ps when the temperature increases from T = 10 to 280 K. RT electron spin relaxation as long as 25 ns has also been measured by electron paramagnetic resonance ͑EPR͒ spectroscopy in colloidal n-doped ZnO quantum dots. 6 To the best of our knowledge, neither the exciton nor the hole spin dynamics in ZnO have been measured yet. Indeed two experimental issues arise: ͑i͒ the small value of the spinorbit coupling energy ͑9-16 meV͒ ͑Refs. 7 and 8͒ imposes resonant optical excitation conditions 9 in the near UV to create an exciton spin polarization; ͑ii͒ the direct measurement of the free hole spin relaxation by pump-probe experiments would require the fabrication of stable p-doped samples, 10,11 which remains a challenge in ZnO ͑Ref. 12͒. In order to investigate the hole spin dynamics in ZnO, we have studied the polarization properties of the exciton bound to neutral donors. Since this complex consists of a singlet of electrons and a hole, its spin polarization is directly determined by the orientation of the hole bound in the complex. [13][14][15] ZnO crystallizes in the wurtzite phase, where the hexagonal crystal field ⌬ cr and the spin-orbit coupling ⌬ so give rise to three doubly degenerated valence bands, labeled A, B, and C. The optical selection rules and oscillator strengths impose that only the transitions from the A and B valence bands are optically allowed when the light propagates along the c axis of the crystal. 7,8,13 We present in this paper a detailed investigation of the optical orientation of excitons and holes in ZnO bulk and epilayer samples. By time-resolved photoluminescence ͑PL͒ experiments, we evidence the fast free exciton spin relax-ation ͑ FX s Ͻ 10 ps͒ and we measure the hole spin relaxation time ͑up to h s ϳ 350 ps͒ in the donor-bound exciton complex.The samples under investigatio...