We report the DNA photocleavage abilities of GEO30 and GEO31, near-infrared (NIR) donor-π-acceptor fluorophores (D-π-A) with a chloroacrylic acid acceptor linked to an indole donor group via a π-conjugated linker containing a cyclohexene and a meso-chlorine atom. We are interested in developing these fluorophores as NIR photosensitizers (PS) in photodynamic therapy (PDT). UV-visible spectrophotometry studies showed that GEO30 and GEO31 were unstable in aqueous buffer but exhibited stable DNA interactions. Competitive DNA binding results using pentamidine and methyl green indicated that dyes GEO30 and GEO31 possibly bind in the minor and major grooves of DNA. In the absence and presence of a fluorescent probe and chemical additives, the irradiation of the dyes with a 750 nm LED medical lamp was shown to generate Type I hydroxyl radicals that formed direct DNA cleavage in high yields (pH 7.0, 10 °C).