From the perspective of green growth, which seeks to coordinate and make sustainable the development of resources, the environment, and the economy, this study's aim was to find out whether the high-tech industry along the Belt and Road (B&R) is sustainable and effective in using resources, reducing environmental pollution, and increasing performance. This study used panel data covering 16 provinces (municipalities) along the B&R in China between 2009 and 2016. This study used the directional distance function (DDF) and the global Malmquist-Luenberger (GML) index model to analyze the technological innovation efficiency (TIE) of the high-tech industry (HTI) while considering the undesirable output (environmental pollution). Further, supplemented by ArcGIS geographical analysis, this study carried out a comparative analysis of the TIE and its decomposition in the HTI along the B&R from geographical and time-series dimensions. Moreover, the panel Tobit regression model was used to analyze the influencing factors of TIE. The results show that the direct financial support of the government has no impact on the improvement of TIE in the HTI, the government's regulation of environmental pollution can significantly affect the improvement of the TIE, the intensity of R&D has a significantly negative impact on the TIE, a higher level of R&D personnel in the HTI can be helpful in improving TIE, and increasing the import and export trade volumes of the HTI can promote TIE.