Graphene ultrathin films were synthesized by means of solid-state carbon diffusion from amorphous carbon (a-C) thin layers deposited on silicon substrates, which was catalyzed by nickel layers coated on the top of the a-C layers. The graphene films were used as working electrodes that were modified by a polyaniline (PANI) porous layer together with in-situ deposited bismuth (Bi) nanoparticles for the detection of trace heavy metal ions (Pb2+ and Cd2+) in acetate buffer solutions (pH 5.3) with square wave anodic stripping voltammetry. The graphene electrodes modified with PANI porous layers and Bi nanoparticles had excellent repeatability, ultrahigh sensitivity (as low as 0.33 nM) and good resistance to passivation caused by the surface active species adsorbed on the electrode surfaces. (C) 2013 Elsevier B. V. All rights reserved.