Iso-iodoform (iso-CHI2–I) species which is produced during iodoform (CHI3) photolysis in solution have been extensively studied but direct structural information of such isomer remains elusive. In this study, photodissociation dynamics of CHI3 in cyclohexane solvent as well as the structure of iso-CHI2–I were monitored by time-resolved X-ray liquidography(TRXL). A 267 nm femtosecond laser pulse was used to induce C-I bond cleavage of CHI3 and subsequent X-ray probe pulse was irradiated to CHI3 solution to give time-dependent diffraction pattern which contains structural information of photoproducts. Both iso-CHI2 –I and CHI2· are formed within 100 ps and the lifetime of iso-CHI2-I was measured as 330 ns. Iodine radical (I·) is also formed during the course of the iodoform photolysis, which can either recombines nongeminately with CHI2· or I· with bimolecular rate constant of 7.6 × 109 M-1s-1 and 1.5 × 1010 M-1s-1 respectively. Based on our structure analysis, I-I distance and C-I-I angle of iso-CHI2–I were determined as 2.922 ± 0.004 Å and 133.9 ± 0.8° respectively.