Metal-organic charge-transfer complexes based on TCNQ shows exciting electrical or photochemical switching properties, which involves modification of the valence state of TCNQ (TCNQ-/TCNQ°). We use complementary microspectroscopic tools to investigate in-situ the switching behaviour of individual Ag-TCNQ nanocrystals. Structural probes like Nano-XRD and electron diffraction are considered to offer insight into potential structural modifications upon electrical switching.