The objective of this study is to explore the impact of electronic commerce on employment rate for a sample covering the whole 27 Member States of the European Union (EU-27), from 2010 to 2019. Moreover, this research explores the clusters of nations with reference to electronic commerce adoption and employment rate dynamics. The outcomes of cluster analysis show that Western Europe reveals the most developed e-commerce marketplace in EU-27, shown by Internet accessibility and high penetration rate of digital tools, and the lowest figures are registered in the Eastern part of Europe. Furthermore, the empirical findings of the panel data fixed-effects and the generalized least squares regressions suggest that electronic commerce influences employment rate positively. By including country-level control variables (real GDP growth rate, research and development expenditure, employed ICT specialists, enterprises with Internet access), the outcomes reveal that one percentage change in enterprises’ total turnover from e-commerce sales, enterprises’ turnover from web sales, and enterprises with e-commerce sales of at least 1% turnover will increase employment rate by 0.205, 0.258, and 0.350 percentage points. Furthermore, the econometric evidence from the method of moments quantile regression models with fixed effects reinforces our findings. Enterprises’ total turnover from e-commerce sales and the percentage of enterprises with e-commerce sales of at least 1% turnover positively influence employment rate for all quintiles, but in the case of enterprises’ turnover from web sales, the effect is positive only for the quintiles ranging from 0.5–0.8.