A wide range of urban ecosystem studies, including urban hydrology, urban climate, land use planning and watershed resource management, require accurate and up‐to‐date geospatial data of urban impervious surfaces. In this study, the potential of the synergistic use of optical and InSAR data in urban impervious surface mapping at the sub‐pixel level was investigated. A case study in Hong Kong was conducted for this purpose by applying a classification and regression tree (CART) algorithm to SPOT 5 multispectral imagery and ERS‐2 SAR data. Validated by reference data derived from high‐resolution colour‐infrared (CIR) aerial photographs, our results show that the addition of InSAR feature information can improve the estimation of impervious surface percentage (ISP) in comparison with using SPOT imagery alone. The improvement is especially notable in separating urban impervious surface from the vacant land/bare ground, which has been a difficult task in ISP modelling with optical remote sensing data. In addition, the results demonstrate the potential to map urban impervious surface by using InSAR data alone. This allows frequent monitoring of world's cities located in cloud‐prone and rainy areas.