We present a highly reliable and efficient mid-infrared colour-based selection technique for luminous active galactic nuclei (AGN) using the Wide-field Infrared Survey Explorer (WISE) survey. Our technique is designed to identify objects with red mid-infrared power-law spectral energy distributions. We studied the dependency of our mid-infrared selection on the AGN intrinsic luminosity and the effectiveness of our technique to uncover obscured AGN missed in X-ray surveys. To do so we used two samples of luminous AGN independently selected in hard X-ray and optical surveys. We used the largest catalogue of 887 [OIII]5007-selected type 2 quasars (QSO2s) at z<0.83 in the literature from the Sloan Digital Sky Survey (SDSS), and the 258 hard (>4.5 keV) X-ray-selected AGN from the Bright Ultrahard XMM-Newton Survey (BUXS). The effectiveness of our mid-infrared selection technique increases with the AGN luminosity. At high luminosities and at least up to z~1 our technique is very effective at identifying both Compton-thin and Compton-thick AGN.