FOr starters, CH4 + 3O2=CO2 +2 H2O.
Methane (CH4) is the shortest of the hydrocarbons, but this little bit of stoichiometry is provided to illustrate that the burning of hydrocarbons inevitably releases Carbon Dioxide and water. The more hydrocarbons burned, the more Carbon Dioxide and water released.
Since our most common motor fuel is a hydrocarbon blend, this is to be expected.
In general more vehicles, more Carbon Dioxide.
Or they could run electric vehicles, the vast majority of which will use electricity created by burning carbon based fuels ( liquid, gas, or solid), which will release CO2 also.
Or, we could just have people ride bicycles or walk, and exhale more CO2 from the exertion.
It seems no matter what is done, though, the more energy used, the more CO2 will be released.