A strategic methodology has been developed to effectively synthesize the fac-[Re(CO)(3)(dcbH(2))(trans-stpy)](+) complex, where dcbH(2) = 2,2'-bipyridine-4,4'-dicarboxylic acid and trans-stpy = trans-4-styrylpyridine, which has been designed to efficiently absorb visible light. The complex exhibits outstanding trans-to-cis photoisomerization with 436 nm irradiation (Phi(trans -> cis) = 0.50 +/- 0.03), in contrast to the photochemical behavior previously reported in the literature (Faustino, L. A.; et al. Inorg. Chem. 2018, 57, 2933-2941). The main emphasis here is to address the synthetic strategy for obtaining the actual complex, its characterization, and an accurate description of its photochemical and photophysical behavior, which reveal new insights into this complex.