High-purity NiO/ Al 2 O 3 catalysts were prepared by mixing NiO and ␥-Al 2 O 3 nanopowders. X-ray diffraction patterns were measured to characterize the grain size and crystalline phase of the nanopowders. Positronannihilation spectroscopy was used to study the microstructure and surface properties of the pores inside the NiO/ Al 2 O 3 catalysts. The positron lifetime spectrum comprises two short and two long lifetime components. The two long lifetimes 3 and 4 correspond to ortho-positronium ͑o-Ps͒ annihilated in microvoids and large pores, respectively. With increasing NiO content in the NiO/ Al 2 O 3 catalysts, both 4 and its intensity I 4 show continuous decrease. Meanwhile, the para-positronium ͑p-Ps͒ intensity, obtained from coincidence Doppler broadening spectra, increases gradually with NiO content. The different variation in o-Ps and p-Ps intensity suggests the ortho-para conversion of positronium in NiO/ Al 2 O 3 catalysts. X-ray photoelectron spectroscopy shows that Ni mainly exists in the form of NiO. The electron-spin-resonance measurements reveal that the ortho-para conversion of Ps is induced by the unpaired electrons of the paramagnetic centers of NiO.