In this work, the outlying decoration of the free-base meso-(4-tetra) pyridyl porphyrin (H₂TPyP) with the RuCl(dppb)(5,5′-Me-bipy) ruthenium complex (here named Supra-H₂TPyP) is observed as an improved molecular photocatalyst for dye-mediated chloroform (CHCl₃) decomposition via one-photon absorption operating in the visible spectral range (532 nm and 645 nm). Supra-H₂TPyP offers a better option for CHCl₃ photodecomposition when compared to the same process mediated by pristine H₂TPyP, which requires either excited-state- or UV absorption. The chloroform photodecomposition rates for Supra-H₂TPyP as well as its excitation mechanisms are explored as a function of distinct laser irradiation conditions.