The fabrication of nanostructured films with tailored properties is essential for many applications, particularly with materials such as polyaniline (PANI) whose electrical characteristics may be easily tuned. In this study we report the one-step synthesis of AgCl–PANI nanocomposites that could form layer-by-layer (LbL) films with poly(sodium 4-styrenesulfonate) (PSS) and be used for electronic tongues (e-tongues). The first AgCl–PANI layer was adsorbed on a quartz substrate according to a nucleation-and-growth mechanism explained using the Johnson–Mehl–Avrami (JMA) model, revealing a 3D film growth confirmed by atomic force microscopy (AFM) measurements for the AgCl–PANI/PSS LbL films. In contrast to conventional PANI-containing films, the AgCl–PANI/PSS LbL films deposited on interdigitated electrodes exhibited electrical resistance that was practically unaffected by changes in pH from 4 to 9, and therefore these films can be used in e-tongues for both acidic and basic media. With a sensor array made of AgCl–PANI/PSS LbL films with different numbers of bilayers, we demonstrated the suitability of the AgCl–PANI nanocomposite for an e-tongue capable of clearly discriminating the basic tastes from salt, acid and umami solutions. Significantly, the hybrid AgCl–PANI nanocomposite is promising for any application in which PANI de-doping at high pH is to be avoided.