An urban ecological zone (UEZ) is an important part of a city, focusing on environmental conservation and ecological economic development simultaneously. During the past decade, the urban scale of Xi’an city in China has been expanding, and the population has been increasing rapidly. This dramatic change is a huge challenge to urban sustainability. It puts forward higher requirements for the construction of an UEZ. Under different spatial resolution scales, this study adopted Landsat8-OLI and gaofen-2 (GF-2) satellite high-resolution remote sensing data to interpret the land use/cover change (LUCC) of the Weihe River UEZ. The ecosystem service value (ESV) was assessed, and the ecological effect was analyzed based on LUCC. The results showed that the spatial distribution of land types in the Weihe River UEZ changed significantly from 2014 to 2020. The construction land gathered to the southeast. Especially, the vegetative land (i.e., forestland, grassland and other green land) and water body showed a slightly increasing trend since the official establishment of the UEZ in 2018. The cultivated land area gradually reduced, and the vegetative land area tended to be concentrated as well as expanded. Through the interpretation of GF-2 remote sensing data, the ESV at the Weihe River UEZ showed a downward trend in general. The high-value areas were mainly distributed in the Weihe River and its surrounding beach areas, which were greatly affected by river water scope. Construction land normally had low ESV, and it was affected by human activities obviously. Therefore, the development of urban construction had significant impacts on the Weihe River UEZ.