Time-of-flight mass spectrometry and the photoion-photoion coincidence technique have been used to study dissociative single and double photoionization processes of CF 4 in the energy range of 23-120 eV together with linearly polarized synchrotron radiation. Under the condition where the molecular and dissociative single and double photoionization processes take place concomitantly, we have explicitly determined the ion branching ratios for single photoionization. Together with previously reported data for the ion branching ratios of ion-pairs and doubly charged ions in double photoionization, we have derived the ratio of double to single photoionization (σ 2 + /σ + ), the partial cross-sections for single (σ + ) and double (σ 2 + ) photoionization, the ionization yield and the partial cross-sections for the individual fragment ions produced from the singly and doubly charged parent ions, CF 4 + and CF 4 2 + . Dissociation pathways of CF 4 are discussed on the basis of the observed ion branching ratios and the derived partial photoionization cross-sections of fragment ions and ion-pairs.