Coulomb-excitation experiments are performed with postaccelerated beams of neutron-deficient Po196,198,200,202 isotopes at the REX-ISOLDE facility. A set of matrix elements, coupling the low-lying states in these isotopes, is extracted. In the two heaviest isotopes, Po200,202, the transitional and diagonal matrix elements of the 2+1 state are determined. In Po196,198 multistep Coulomb excitation is observed, populating the 4+1,0+2, and 2+2 states. The experimental results are compared to the results from the measurement of mean-square charge radii in polonium isotopes, confirming the onset of deformation from Po196 onwards. Three model descriptions are used to compare to the data. Calculations with the beyond-mean-field model, the interacting boson model, and the general Bohr Hamiltonian model show partial agreement with the experimental data. Finally, calculations with a phenomenological two-level mixing model hint at the mixing of a spherical structure with a weakly deformed rotational structure.