In this paper, by treating the cosmological constant as a thermodynamic pressure, we study the thermodynamics and phase transitions of the dyonic AdS black holes in Gauss-Bonnet-Scalar gravity, where the conformal scalar field is considered. In a more general extended phase space, we first verified the first law of black hole thermodynamics, and find that it is always true. Meanwhile, the corresponding Smarr relation is also obtained. Then, we found that this black hole exhibits interesting critical behaviors in six dimensions, i.e., two swallowtails can be observed simultaneously. Interestingly, in a specific parameter space, we observed the small/intermediate/large black hole phase transitions, with the triple point naturally appearing. Additionally, the small/large black hole phase transition, similar to the liquid/gas phase transition of the van der Waals fluids, can also be found in other parameter regions. Moreover, we note that the novel phase structure composed of two separate coexistence curves discovered in the dyonic AdS black holes in Einstein-Born-Infeld gravity disappears in Gauss-Bonnet-Scalar gravity. This suggests that this novel phase structure may be related to gravity theory, and importantly, it is generally observed that the triple point is a universal property of dyonic AdS black holes. On the other hand, we calculated the critical exponents near the critical points and found that they share the same values as in mean field theory. Finally, it is true that these results will provide some deep insights into the interesting thermodynamic properties of the dyonic AdS black holes in the background of conformal scalar fields.