The development of near-infrared light (NIR)-responsive conductive polymers provides a useful theranostic platform for malignant tumours by maximizing spatial resolution with deep tissue penetration for diagnosis and photothermal therapy. Herein, we demonstrated the self-assembly of ultrathin two-dimensional (2D) polypyrrole nanosheets utilizing dopamine as a capping agent and a monolayer of octadecylamine as a template. The 2D polypyrrole-polydopamine nanostructure (DPPy) had tunable size distribution which showed strong absorption in the first and second near-infrared windows, enabling photoacoustic imaging and photothermal therapy. The hybrid double-layer was demonstrated to increase Raman intensity for 3D Raman imaging (up to two orders of magnitude enhancement and spatial resolution up to 1 μm). The acidic environment drove reversible doping of polypyrrole, which could be detected by Raman spectroscopy. The combined properties of the nanosheets could substantially enhance performance in dual-mode Raman and photoacoustic guided photothermal therapy, as shown by the 69% light to heat conversion efficiency and higher cytotoxicity against cancer spheroids. These pH-responsive features highlight the potential of 2D conductive polymers for applications in accurate, highly efficient theranostics.