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The achievement of nanometer spatial resolution with direct elemental selectivity would have a tremendous impact on our ability to probe and understand complex phenomena occurring at the nanoscale. The combination of synchrotron-based X-ray spectroscopy with the high spatial resolution of scanning tunneling microscopy (STM) has the potential to help attain this goal. In this chapter we show how synchrotron X-ray-enhanced scanning tunneling microscopy (SXSTM) has evolved from the very early days of photo-assisted STM to become a promising spectroscopy and imaging technique in nanoscience and nanotechnology. The basic principles of SXSTM are discussed accompanied by a presentation of recent experiments. [ABSTRACT FROM AUTHOR]