This paper reports on progress in the VUV spectroscopy of surfaces and nanostructures, as facilitated by two experimental innovations. In Scanning Probe Energy Loss Spectroscopy (SPELS) electrons backscattered from the tipsurface junction are detected when an STM tip is operated in field emission mode. Energy loss features in the range 1300 eV have been observed, corresponding to optical absorption spectra from the IR through to the VUV and X-ray regions. Recent data suggests in addition that SPELS can record local secondary electron emission spectra. SPELS offers spatial resolution on the 10 nm scale. High Harmonic Generation (HHG) of VUV light provides a complementary probe of the excited states of surfaces and nanostructures, offering a temporal resolution of order 100 fs or below. The utility of the High Harmonic source is demonstrated by an investigation of the visible fluorescence from thin films of passivated CdSe nanocrystals, as a function of excitation energy, decay time and temperature, which thus emerge as new scintillators for VUV applications.