Broadband (λ > 320 nm) irradiation of (Bu4N)2Pd2Br6 in chloroform causes the conversion of Pd2Br62- to Pd2Cl62-. During the conversion, chloroform is decomposed photocatalytically at a rate that accelerates then decelerates as coordinated bromines are replaced by chlorines. The primary bromine-containing product is CCl3Br. The observations are consistent with a mechanism in which Pd2Br62- and the intermediate Pd2Br6-nCln2- complexes undergo homolytic photodissociation of a bromine or chlorine atom, which terminates with a trichloromethyl radical or abstracts a hydrogen from chloroform, respectively.