Using the close relationship between the low-energy constants of chiral perturbation theory and the chiral invariant interactions of the vector meson resonances with the pseudoscalar mesons, we investigate the process rho(0) --> pi(+)pi(-)gamma. Compared with the contribution from the pure bremsstrahlung mechanism, we find an enhancement of the decay rate near the endpoint of the photon energy spectrum. Such a particular shape of the differential decay rate has indeed been observed experimentally and turns out to be an important confirmation of the theoretical concept of chiral vector meson dominance.