The spectral distribution of the 1s2s {1}S{0}-->1s{2} 1S0 two-photon decay of He-like tin was measured using a novel approach at the gas-jet target of the ESR storage ring. Relativistic collisions of Li-like projectiles with low-density gaseous matter have been exploited to selectively populate the desired 1s2s state. Compared to conventional techniques, this approach results in a substantial gain in statistical and systematic accuracy, which allowed us to achieve for the first time a sensitivity to relativistic effects on the two-photon decay spectral shape as well as to discriminate the measured spectrum for Sn from theoretical shapes for different elements along the He-isoelectronic sequence.