The development of metal-free organic room temperature phosphorescence (RTP) materials has attracted increasing attention because of their applications in sensors, biolabeling (imaging) agents and anticounterfeiting technology, but remains extremely challenging owing to the restricted spin flip intersystem crossing (ISC) followed by low-yield phosphorescence that cannot compete with nonradiative relaxation processes. Here, we report a facile strategy to realize highly efficient RTP by doping iodo difluoroboron dibenzoylmethane (I-BF(2)dbm-R) derivatives a rigid 4-iodobenzonitrile (Iph-C N) matrix. We found that halogen bonding between cyano group of Iph-C N matrix and iodine atom of I-BF(2)dbm-R dopant is formed in doped crystals, i.e., Iph-C N center dot center dot center dot I-BF(2)dbm-R, which not only suppresses nonradiative relaxation of triplets but also promotes the spin orbit coupling (SOC). As a result, the doped crystals show intense RTP with an efficiency up to 62.3%. By varying the substituent group R in I-BF(2)dbm-R from electron donating -OCH3 to electron accepting -F, -CN groups, the ratio between phosphorescence and fluorescence intensities has been systematically increased from 3.8, 15, to 50.