Humite group minerals occur in the marbles of granulite grade at Ambasamudram, southern India. Detailed mineralogical and mineral chemical characterization indicate the mineral is a flourine-rich titanian-poor variety of clinohumite. Average MTi/Si values of 2.22 with typical XRD pattern indicate the mineral to be clinohumite. Petrological constraints on the clinohumite formation shows a high temperature (>700°C) and low aco2 during its formation. The fluorine content of these clinohumites is the highest reported in any environment, with F/(F+OH) ratio reaching a value of 0.70. The high fluorine content reflect the high P-T condition of formation. The OH content of the clinohumites is around 0.59 mole fraction. Preliminary FTIR spectra of the clinohumites show eight sharp absorption peaks between wave numbers 3700 and 3400 cm−1 and a broad absorption band with a peak at 3840 cm−1. The sharp peaks are due to OH in the clinohumite. The high fluorine content of the Ambasamudram clinohumites possibly resulted from the isochemical reactions involving (OH-F) silicates such as amphiboles or phlogopites. The internal fluid buffering is also supported by the stable isotope as well as the petrological studies of the marble assemblages.