We report on Langmuir-Blodgett (LB) films made with emeraldine salt polyaniline (PAni-ES) and organophilic montmorillonite clay mineral (OMt), where synergy between the components was reached to yield an enhanced performance in detecting trace levels of cadmium (Cd2+), lead (Pb2+) and copper (Cu2+). Detection was carried out using square wave anodic stripping (SWAS) voltammetry with indium tin oxide (ITO) electrodes modified with LB films of PAni-ES/OMt nanocomposite, whose data were compared to those obtained with electrodes coated with neat PAni-ES and neat OMt LB films. The enhanced performance in the nanocomposite may be attributed to the stabilizing and ordering effect promoted by OMt in PAni-ES Langmuir films, which then led to more homogeneous LB films. According to X-ray diffraction data, the stacking of OMt layers was preserved in the LB films and therefore the PAni-ES chains did not cause clay mineral exfoliation. Instead, OMt affected the polaronic state of PAni-ES as indicated in UV-vis, Raman and FTIR spectra, also consistent with the changes observed for the Langmuir films. Taken together these results do indicate that semiconducting polymers and clay minerals may be combined for enhancing the electrical properties of nanostructures for sensing and related applications. ; Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) ; Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) ; Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)