A detailed analysis of the radiative pp annihilation is made in the framework of a two-step formalism, the pp annihilates into meson channels containing a vector meson with a subsequent conversion into a photon via the vector dominance model (VDM). Both steps are derived from the underlying quark model. First, branching ratios for radiative protonium annihilation are calculated and compared with data. Then, details of the isospin interference are studied for different models of the initial protonium state and also for different kinematical form factors. The isospin interference is shown to be uniquely connected to the pp − nn mixing in the protonium state. Values of the interference terms directly deduced from data are consistent with theoretical expectations, indicating a dominant pp component for the 1 S 0 and a sizable nn component for the 3 S 1 protonium state. The analysis is extended to the pp → γΦ transition, where the large observed branching ratio remains unexplained in the VDM approach.