There is evidence for high  concentrations of over 6,000 ppm between 600 and 400 million years ago, and of over 3,000 ppm between 200 and 150 million years ago.
Indeed, higher CO concentrations are thought to have prevailed throughout most of the Phanerozoic Eon, with concentrations four to six times current concentrations during the Mesozoic era, and ten to fifteen times current concentrations during the early Palaeozoic era until the middle of the Devonian period, about 400 million years ago. The spread of land plants is thought to have reduced CO concentrations during the late Devonian, and plant activities as both sources and sinks of CO have since been important in providing stabilizing feedbacks. 
Earlier still, a 200-million year period of intermittent, widespread glaciation extending close to the equator (Snowball Earth) appears to have been ended suddenly, about 550 Ma, by a colossal volcanic outgassing that raised the  concentration of the atmosphere abruptly to 12%, about 350 times modern levels, causing extreme greenhouse conditions and carbonate deposition as limestone at the rate of about 1 mm per day. This episode marked the close of the Precambrian Eon, and was succeeded by the generally warmer conditions of the Phanerozoic, during which multicellular animal and plant life evolved. No volcanic CO emission of comparable scale has occurred since. In the modern era, emissions to the atmosphere from volcanoes are approximately 0.645 billion tons of  per year, whereas humans contribute 29 billion tons of  each year.