We present a method for accurate determination of atomic transition matrix elements at the 10 −3 level. Measurements of the ac Stark (light) shift around "magic-zero" wavelengths, where the light shift vanishes, provide precise constraints on the matrix elements. We make the first measurement of the 5s-6p matrix elements in rubidium by measuring the light shift around the 421 nm and 423 nm zeros with a sequence of standing wave pulses. In conjunction with existing theoretical and experimental data, we find 0.3236(9) ea0 and 0.5230(8) ea0 for the 5s-6p 1/2 and 5s-6p 3/2 elements, respectively, an order of magnitude more accurate than the best theoretical values. This technique can provide needed, accurate matrix elements for many atoms, including those used in atomic clocks, tests of fundamental symmetries, and quantum information.