According to officials, the fiery eruption of red rocks and lava happened at approximately 3am local time (about 8am GMT). Incandescent rock reached up to 400 metres (1,310 feet) in the air and ash spread some 2 kilometres (1.2 miles) south into the night sky.
Deposits of ash was registered in the regions of Ozumba, Ecatzingo and Tepetlixpa.
Authorities have warned residents of affected communities to cover their nose and mouth and refrain from outdoor activity. Emergency officials are policing a 12 km exclusion zone around the 9,500-km-high (5,900-mile-high) volcano.
Popocatepetl is one of Mexico’s most active volcanoes with more than a dozen significant explosions registered since the arrival of the Spanish in 1519.