Prompt gamma rays have been observed for the first time from the neutron-deficient nucleus Po-191 using the recoil-decay tagging technique at the RITU gas-filled separator. In addition improved alpha decay data have been measured for Po-191 and its daughter product Pb-187. The complementary gamma- and alpha-decay data point to the onset of oblate deformation in the light odd-mass Po nuclei by approaching the neutron midshell at N=104. The pattern of the favored and unfavored states observed on top of the 13/2(+) isomer in Po-191 indicates a change from the weak-coupling towards the strong-coupling scheme in Po-191m. In the daughter nucleus Pb-187, the 13/2(+) and 3/2(-) isomeric states become degenerate within the experimental accuracy. Evidence for triple shape coexistence at low energy has been found in the high-spin isomer in Pb-187. The results are supported by potential-energy surface calculations and by particle-plus-rotor calculations.