Photoinduced linkage isomers (PLIs) of NO and NO 2 − are selectively generated by an appropriate choice of irradiation wavelength at low temperature within the same molecular complex Rh(NO)(NO 2 ) 2 (Bu t 2 PH) 2 . The structures of the PLIs are characterised by photocrystallography and the corresponding vibrational changes by infrared spectroscopy. Using red light about 37% of the κON isonitrosyl PLI can be produced while irradiation with blue light produces about 80% of the (O,O′) chelating NO 2 − isomer. Upon heating the NO 2 − PLI undergoes several structural transformations, which are characterised by infrared spectroscopy. Photoinduced linkage isomers (PLIs) of NO and NO 2 − are selectively generated by an appropriate choice of irradiation wavelength at low temperature within the same molecular complex Rh(NO)(NO 2 ) 2 (Bu t 2 PH) 2 .