Abstract The synthesis and characterisation of three novel iridium(III) bis‐cyclometallated complexes is reported. Their photophysics have been fully characterised by classical methods and revealed charge‐transfer (CT) and ligand‐centred (LC) transitions. Their ability to selectively interact with G‐quadruplex telomeric DNA over duplex DNA has been studied by circular dichroism (CD), bio‐layer interferometry (BLI) and surface plasmon resonance (SPR) analyses. Interestingly, one of the complexes was able to promote photoinduced electron transfer (PET) with the guanine DNA base, which in turn led to oxidative damage (such as the formation of 8‐oxoguanine) to the telomeric sequence. To the best of our knowledge, this is the first study of highly photo‐oxidising bis‐cyclometallated iridium(III) complexes with G‐quadruplex telomeric DNA.