In the flash photolysis of thiazole at low pressure without any diluent, the 0–0, 1–1 and 0–1 bands of the CN violet system were observed in absorption; the 0–0 band at 3883·4 A showed a high rotational excitation corresponding to a temperature of ⋍2000 K. The addition of argon makes the NCS bands appear with good intensity and at the same time relaxes the CN rotationally and vibrationally. These observations suggest that highly excited NCS is initially formed in the photodecomposition of thiazole which acted as a precursor to the rotationally and vibrationally excited CN radical. This paper deals with studies on the effect of argon on the relative intensities of CN and NCS and on the non-thermal rotational and vibrational intensity distribution of the CN violet system. The mechanism of formation of rotationally unrelaxed CN in the flash photolysis of thiazole has been proposed.