Optical reflectance (OR) and electro-reflectance (ER) spectroscopies were employed to study the resonant optical properties of GaAs/AlGaAs multiple quantum wells based Resonant Bragg Structures (RBS) at excited states. The RBS samples have 60 periods of GaAs/AlGaAs quantum well/barrier grown on semi-insulating GaAs substrates by molecular beam epitaxy with slightly different thicknesses of well/barrier. We observed enhanced OR and ER features when exciton energy coincides with the energy of the Bragg reflection peak, a double resonance condition. Bragg peak can significantly be tuned by changing the angle of incidence of the light. Exciton energies can be tuned by changing the temperature, external electric field and the thickness of the quantum wells. By tuning the Bragg peak for double resonance in the RBS samples of different thicknesses, we observed the electro-reflectance features related to the transitions of x(e2-hh2), x(e2-hh1), x(e2-lh1), x(e2-hh3) and x(e1-hh3) excitons along with the sharp features of x(e1-hh1) and x(e1-lh1) ground state exciton transitions from the ER experiments. The excitonic transitions x(e2-hh1), x(e2-lh1) and x(e2-hh3) which are prohibited at zero electric field, were also observed due to the increased overlap of the electron and hole wave functions caused by the electric field; built-in electric field or applied DC bias.