CuI/polyaniline (PANI) nanocomposites with novel structure were successfully synthesized using CuSO₄ as the oxidant for aniline in the presence of KI. The morphology of the composites can be controlled by adjusting the reaction conditions. Remarkably, the nanocomposite films display excellent superhydrophobicity without further modification by low-free energy materials. The static contact angle (CA) for water on the surface of the resulting nanocomposites is over 160°. The special wettability is attributed to the novel structure of the CuI/PANI nanocomposites with high roughness. Moreover, for the first time, the photocatalytic property of the as-synthesized CuI/PANI nanocomposites has been studied, showing that they display excellent photocatalytic activity for the degradation of rhodamine B (RhB) under visible light irradiation. It is attributed to a synergic effect between PANI and CuI. According to the experimental results, a photocatalytic mechanism is proposed. The developed nanocomposites could have potential applications in superhydrophobic coatings, decontamination corrosion prevention, radiation proofing and so on.