Abstract: The issue ofclimate change is the focus of international community. CO₂ emissions from the combustion of fossil fuel contributed more than 58% to total greenhouse gas(GHGs) emissions, which is the main source of GHGs emissions, and it is also the main focus of GHGs emissions reduction in every country. Therefore, the accuracy of CO₂ emission accounting of fossil fuel combustion is the basis for the formulation and implementation of emission reduction policies. The difference between different accounting methods mainly lies in the choice of emission factors. The national greenhouse gas inventory report is an official document submitted to the United Nations by the states parties to the Paris agreement, which consists of the national inventory report (NIR) and common reporting format (CRF). In this study, the greenhouse gas inventory report submitted by annex I countries was collated. And the dataset of CO₂ emission factors of fossil fuels combustion by Sectoral-approach in annex I countries from 1990 to 2016 was obtained and classified. The dataset is the xlsx file which contains country data and aggregated data, and it is convenient for data retrieval, filtering, comparison and analysis. It can be used as the basic data for subsequent greenhouse gas accounting.