Abstract: The volcanic eruptions are one of the most characteristic natural sources of CO2 in the atmosphere (IPCC, 1990, 2007). In order to study the effect of volcanic eruptions on the increased levels of CO2, we have used data from the Basic Environmental Observatory (BEO) “Moussala”, Bulgaria, for the period comprised between July 2007 and March 2015. The Carbon dioxide is not a health hazard gas and there is no established limit concentration by the Bulgarian and international law. In this study, we have accepted as extremely high values the values that exceed the 95th percentile of the distribution of the daily average values for the studied period. The days with exceeding CO2 concentration were analysed in terms of volcanic activity (Etna), which could affect the investigated area with the spread of air pollutants and also CO2. The simulations developed by the Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) Model are used in order to describe the trajectory and dispersion of pollutant and products from eruptions of Etna in the atmosphere. A synchrony between the occurrence of days with extreme high concentration of CO2 in the atmosphere in the region of BEO “Moussala” and eruptions of Etna volcano was established in most of the investigated cases.The analysis of the results from BEO “Moussala” confirms the impact of the volcanic eruptions and Etna volcano, in particular, for the increasing of CO2 concentration in the atmosphere. On the other side, it was established that the activity of Etna is not the only factor which has impact on the concentration of CO2. More detailed analyses concerning not only natural, but also anthropogenic factors have to be done in the future in order to clarify the reasons for the increasing concentration of CO2 in the atmosphere (IPCC, 2014).