In this paper we study a phase structure of 5D N = 1 super Yang-Mills theory with massive matter multiplets and SU(N ) gauge group. In particular, we are interested in two cases: theory with N f massive hypermultiplets in the fundamental representation and theory with one adjoint massive hypermultiplet. If these theories are considered on S 5 their partition functions can be localized to matrix integrals, which can be approximated by their values at saddle points in the large-N limit. We solve saddle point equations corresponding to the decompactification limit of both theories. We find that in the case of the fundamental hypermultiplets theory experiences third-order phase transition when coupling is varied. We also show that in the case of one adjoint hypermultiplet theory experiences infinite chain of third-order phase transitions, while interpolating between weak and strong coupling regimes.