The CF3S radical has been investigated using the LIF and fluorescence depletion techniques. The vibrational structure of the first excited (A) over tilde (2)A(1) State has been assigned. The photodissociation process at energies above the origin of the (A) over tilde state has been characterized by fluorescence temporal decay and fluorescence depletion spectroscopy. Above the photodissociation threshold, the ratio of the rates for the competing processes of emission and dissociation varies strongly with both energy and vibrational mode.