Super-knock is one of the major obstacles for improving power density in advanced internal combustion engines (ICE). This work studied the mechanism of super-knock initiation using a rapid compression machine that simulated conditions relevant to ICEs and provided excellent optical accessibility. Based on the high-speed images and pressure traces of the stoichiometric iso-octane/oxygen/nitrogen combustion under high-temperature and high-pressure conditions, it was observed that detonation was first initiated in the near-wall region as a result of shock wave reflection. Before detonation was initiated, the speed of the combustion wave front was less than that of the Chapman–Jouguet (C–J) detonation speed (around 1840 m/s). In the immediate vicinity of the initiation, the detonation speed was much higher than that of the C–J detonation.