We present the first evidence of excitation of the 5p 3/2 → 6p 1/2 electric dipole-forbidden transition in atomic rubidium. The experiments were carried out in a rubidium vapor cell using Doppler-free optical-optical double-resonance spectroscopy with counter-propagating beams. A 5s 1/2 → 5p 3/2 electric dipole preparation step using a diode laser locked to the F = 3 → 4 cyclic transition of the D2 line in 85 Rb is used to prepare the atoms in the first excited state. This is then followed by the 5p 3/2 F 2 = 4 → 6p 1/2 F 3 dipole-forbidden excitation (λ ≈ 917.5 nm) to establish a two-photon ladder (Ξ) excitation scheme. Production of atoms in the 6p 1/2 excited state is verified by detection of the 421 nm fluorescence that results from direct decay into the 5s 1/2 ground state.The polarization dependence of the relative intensities of the lines of the decay fluorescence is also investigated. Experimental data for different polarization configurations of the light beams used in this two-photon spectroscopy are compared with the results of calculations that consider a strong atom-field coupling in the preparation step, followed by a weak electric quadrupole excitation and the blue fluorescence decay emission. Good agreement between experiment and this three-step model is found in the case of linear-linear polarizations.