The China–Europe Railway Express (CRE) plays a crucial role in promoting local economic development and bolstering regional connectivity. Quantitative assessments of urban changes along the CRE are essential for understanding its influence on the local eco-environment and the economy, which is a cornerstone for fostering sustainable growth. Urban boundaries are vital indicators of city development; however, accurately extracting these boundaries over multiple years at a large scale and fine granularity remains challenging. On the basis of a global impervious surface area (GISA2) dataset from 2010 to 2019, this study extracted fine-scaled city boundaries annually for European countries and analyzed the spatiotemporal patterns of urbanization in areas along and not along the express during the past decade. The generated enhanced urban boundaries (EUBs) show strong agreement with the Landsat time-series data and align well with existing global urban time-series products (GUB, GAUD, and NTL). From 2010 to 2019, urban areas and clusters expanded across the entire region, with notable disparities observed between areas along the express (noted as ON-CRE) and those not along (noted as OFF-CRE). ON-CRE cities experienced more substantial urban growth near the express, resulting in new mega urban agglomerations and expansion in small and moderate cities. In contrast, most OFF-CRE cities exhibited stable development with limited urban sprawl. Dynamic proportions of the impervious surface area (ISA) within the EUB indicated more compact impervious areas within ON-CRE boundaries compared to OFF-CRE. This study contributes to understanding urban expansions driven by the long-term CRE operations. The EUB dataset developed herein provides a valuable resource for future investigations into the impacts of urbanization on biotic stress and urban health in European countries, thus supporting the achievement of sustainable development goals.