AbstractThe development of lasing materials with weak pile‐up effect from triplet excitons, low lasing threshold, and long operational lifetime is much significant for truly continuous wave operation and electrically pumping organic lasers. However, most of organic gain media has been verified to have extreme quenching effect from triplet excitons due to its wide‐band distribution of triplet absorption spectrum. Here, it is found that the phenanthroimidazole derivatives as gain media have congenital advantages on handling triplet's issues. A very low amplified spontaneous emission (ASE) threshold of 0.56 µJ cm−2 and a long operational lifetime of 5.77 × 105 pump pulses in air atmosphere are well obtained. When increasing the pump repetition frequency from 20 Hz to 20 kHz, the operational lifetimes of the thin films have small reduction. Under a high pump repetition frequency of 200 kHz, which is quasi‐continuous wave operational regime, the PI2PhDPO thin film exhibits very low ASE threshold of 0.78 µJ cm−2 due to the tiny overlap between triplet absorption and ASE spectra.