Direct solubilization of DNA in organic solvents has attracted growing interest owing to its ability to improve the properties and versatility of DNA in nonaqueous systems, especially when irradiated. In this study, we demonstrate photoinduced DNA solubilization in a chloroform solution containing photoionizable malachite green leuconitrile carrying a long alkyl chain (MGL). Ultraviolet (UV) irradiation of MGL afforded a cationic surfactant, which then interacted with oppositely charged DNA. DNA solubilization in a chloroform/1-hexanol mixture suggested the formation of a DNA-ionized MGL complex. Fluorescence spectroscopy was used to obtain the evidence for the DNA-ionized MGL complex.