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Tourism is one of the important factors that can affect the environmental and economic situation of any economy. This study investigates the relationship between tourist arrivals and CO2 emission in the top 20 tourist destinations using data from quarterly observations from 1995 to 2018. A unique technique via quantile-on-quantile regression and Granger causality in quantiles was used. In particular, how the quantiles of tourist arrivals impact quantiles of CO2 emission was analyzed. The empirical results suggest a combination of both positive and negative effects of tourist arrivals and CO2 emission in most tourist destinations. Predominantly, at both high and low tails, in the USA, Spain, Hong Kong, and Austria, tourist arrival has a positive effect on CO2 emission, whereas in the case of Canada, France, Germany, Mexico, and Malaysia, the association was negative. On the other hand, China, Greece, Russia, Japan, Italy, South Korea, Thailand, and Turkey have both positive and negative effects of tourism on CO2 emissions at low and high tails. Tourism can be an important factor while formulating policy for environmental and climate aspects.