The solvent effects of electro-oxidative deposition of octyl thiolate-stabilized gold nanoparticles with 2.3 +/- 0.5 nm core diameter modified with biferrocene-terminated alkanethiolates on their surface (Au-n-BFc) were investigated using cyclic voltammetry, UV-vis spectroscopy, scanning tunneling microscopy (STM), and electrochemical quartz crystal microbalance (EQCM) techniques. Consecutive potential scans causing two-step one-electron oxidation of the biferrocene units of Au-n-BFc in 0.1 M Bu4NClO4-organic solvent [CH2Cl2, tetrahydrofuran (THF), toluene + acetonitrile (toluene/MeCN; 2:1 v/v)l solution under Ar produced the adhesive Au-n-BFc film on an electrode. The deposition rate was higher in the order THF > toluene/ MeCN > CH2Cl2. The STM images indicated that the films prepared in CH2Cl2 or THF were likely to form domains with similar to80 and 170 nm diameters of the assembled Au-n-BFc's, respectively, as contrast particles were randomly connected in the film deposited in toluene/MeCN. The experimental results all suggested that the electrodeposition process was considerably influenced by solvent properties: the degree of assistance of the chemical reaction of BFc units and the affinity for the charged Au-n-BFc's. By utilizing scanning electrochemical microscopy (SECM), we constructed dot- and line-shape lithographic assemblies of Au-n-BFc particles at a resolution of similar to50-100mum.