The photophysical properties of a few Ir(III) and Rh(III) complexes have been attempted to be correlated (1–4) with their 1O2 generation efficiencies. A very weakly emissive pyrene‐functionalized Ir(III) complex (1) produces 1O2 more efficiently than the other more emissive Ir(III) complexes. All of them have excited triplet state lifetimes (τT) in the microsecond regime. However, the pyrene‐functionalized Ir(III) complex possesses the largest τT and has reasonable HOMO (highest occupied molecular orbital) energy (< –5.51 eV) which is desired for efficient 1O2 production. 1–4 emit mostly from the 3MLCT state. The lowest triplet emissive state of 3 and 4 is the 3MLCT state while it is the 3ILCT/3IL state for 1 which is mostly non‐emissive. However, the large excited state lifetime and the small energy gap between the 3ILCT/3IL states and the ground electronic state for complex 1 facilitates efficient energy transfer to molecular 3O2 producing 1O2.