A novel CrAPO-5 material having a unique microporous–mesoporous hierarchical pore structure (CrAPO-5H) was synthesized using an organosilane surfactant to conventional CrAPO-5 reaction mixture by a one-step hydrothermal process. The materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), N2-adsorption isotherm and UV-visible diffuse reflectance spectroscopy, and employed as a catalyst for the liquid phase oxidation of tetralin. CrAPO-5H produced higher activity than conventional microporous CrAPO-5. Acylperoxy radicals, in situ generated from trimethylacetaldehyde and O2, were more effective as oxidant than tert-butyl hydroperoxide (t-BuOOH); 88% conversion of tetralin with 97% selectivity to 1-tetralone was obtained with the former, whereas 57% conversion with 86% selectivity was achieved using the latter at 80 °C after 8 h. The effect of reaction temperature, Cr content, solvent, and the type of aldehyde employed for the in situ generation of acylperoxy radicals on catalytic performance was investigated. Activities of CrAPO-5H remained constant after 1st catalyst recycle. A hot filtration experiment coupled with a blank test revealed that oxidation proceeded mostly on Cr sites in the CrAPO-5H, but a minor contribution from trace amount of leached Cr could not be ruled out.