Flow-induced vibrations of rigid prisms supported elastically were studied experimentally in a free-surface water channel with a high blockage (2/5). The study focused on finding the prism cross-sectional shape that maximizes the efficiency of energy harvesting. Seven cross-sectional shapes were tested: square, circular, 45° tilted square, equilateral triangle, isosceles 120° triangle, D-section, and C-section. All other dimensionless parameters of the problem, mass ratio, damping, blockage ratio, reduced velocity range, and the Reynolds (Re) number (characteristic velocity times characteristic length divided by kinematic viscosity) range (400–1070), were kept unchanged. By doing so, the effect of the cross-sectional shape was isolated. D-section proved to be the geometry with the highest values of energy transfer efficiency. A hysteresis loop was present in its oscillatory response (dimensionless oscillation amplitude vs reduced velocity). This loop was characterized by two branches, (+) and (−), meaning a bi-valued amplitude response for each reduced velocity. Regarding temporal patterns of wake topology and body motion, it was found that synchronization occurs in the (+) branch, but not in the (−). Regarding vortex shedding modes, particle image velocimetry was used for identification purposes, and it was found that the 2P mode is the dominant mode in the (+) branch, while the 2S mode pervades the (−). Finally, a new relative reduced velocity definition was introduced, and, when re-plotting the experimental results, it was found that the hysteresis loop disappears, thereby providing a more compact mathematical description of the observed phenomena.