By considering the main contributions to the micellar free energy we have analysed the synergistic effect often seen on the CMC of a binary surfactant mixture. The synergistic effects are due mainly to the entropic free energy contributions related with the surfactant head groups. Several cases have been treated: (i) For a mixture of a monovalent ionic and a non-ionic surfactant in the absence of added salt we obtain, entirely because of electrostatic reasons, a negative deviation from the ideal behaviour corresponding to an interaction parameter β≈-1. Upon adding an inert salt we found that the magnitude of the synergistic effect first increases, reaches a maximum and eventually decreases. (ii) For mixtures of two ionic surfactants with the same charge number but with different hydrocarbon moieties β-values as low as -10 may arise. (iii) For mixtures of an anionic and a cationic surfactant enormous effects are anticipated yielding β≤-20 depending on the CMCs of respective pure surfactant. (iv) Synergistic effects due to different cross-section areas of the head groups are found to be rather small, with 0 > β > -1, provided the difference in head group size is modest but can become more significant when the size difference is larger.