The adsorption capacities of new humic acids isolated from Yakouren forest (YHA) and Sahara (Tamenrasset: THA) soils (Algeria) and commercial humic acid (PFHA) on polyaniline emeraldine base (PEB) were studied at pH 6.6. Also the adsorption of heavy metals such as Cd2+, Zn2+ and Ni2+ on humic acid-polyaniline systems (HA-PEB) was investigated at the same conditions. HA-PEB compounds were characterized by scanning electron microscopy (SEM), infrared spectrometry and cavity microelectrode. In addition, batch adsorption and cavity microelectrode were used in the adsorption study of Cd2+, Zn2+ and Ni2+ on HA-PEB. To develop biocaptors of polluting metals using a cavity microelectrode modified by HA-PEB systems, the adsorption kinetic and adsorption capacity were investigated. The SEM analysis showed that the presence of humic acid affected the PEB surface and caused the formation of a granular morphology. The maximum adsorption capacities (q(max)) of PFHA, THA and YHA determined by adsorption isotherms were 91.31, 132.1 and 151.0 mg/g, respectively. Batch adsorption results showed that q(max) of Cd2+, Zn2+ and Ni2+ on HA-PEB followed the order: THA-PEB > YHA-PEB > PFHA-PEB. The voltammograms obtained with HA-PEB modified cavity microelectrode showed the appearance of new redox couples reflecting the adsorption of HA on PEB. Metal-humic acid-polyaniline voltammograms were characterized by appearance of oxidation-reduction couples or reduction wave corresponding to metal. Finally, the result may be exploited to develop a biocaptor based on the cavity microelectrode amended by THA-PEB and YHA-PEB.