Titan, the largest moon of Saturn and similar to Earth in many aspects, has unique orange-yellow colour that comes from its atmospheric haze, whose formation and dynamics are far from well understood. Present models assume that Titan’s tholin-like haze formation occurs high in atmosphere through gas-phase chemical reactions initiated by high-energy solar radiation. Here we address an important question: Is the lower atmosphere of Titan photochemically active or inert? We demonstrate that indeed tholin-like haze formation could occur on condensed aerosols throughout the atmospheric column of Titan. Detected in Titan’s atmosphere, dicyanoacetylene (C4N2) is used in our laboratory simulations as a model system for other larger unsaturated condensing compounds. We show that C4N2 ices undergo condensed-phase photopolymerization (tholin formation) at wavelengths as long as 355 nm pertinent to solar radiation reaching a large portion of Titan’s atmosphere, almost close to the surface.