When gaseous iodine was admitted into the NCl3 autodecomposition flame, intense I(5 2P1⁄2) → I(5 2P3⁄2) emission was observed owing to direct pumping of iodine atoms by NCl3 flame. It is found that the chemical environment of NCl3 flame is benign for I(5 2P3⁄2). The mechanisms of I(5 2P1⁄2) production in the NCl3/I2 reactive gas flow are discussed for the first time. It is believed that Frank–Condon favored E–E energy transfer from Cl2(B) to I(5 2P3⁄2) and the nearly resonant V–E energy transfer from Cl2(X, v=15) to I(5 2P3⁄2) respond for the production of excited state iodine atoms.