Electron transport through individual molecules or ensemble molecules between two metal electrodes has been experimentally measured using various methods such as mercury drop, crossed wire, nanopore, break junctions, and scanning probe microscopy etc. However, there still exist particular difficulties associated with the instability of metal-molecular contacts and possible interactions between multiple molecules in junction. In this work, we report synthesis of unique nanoparticle/single molecules/nanoparticle structures “dimers” (or “trimers”) consisting of ~40 nm (or ~15 nm) gold nanoparticles bridged by oligomeric phenylene ethynylene molecules (OPEs). We also describe the dielectrophoretic assembly method to contact these structures across the nanoscale electrode gaps of ~70 nm (or < 30nm) fabricated by angled metal evaporation technique. The FEMLAB software was used to investigate the electrical field distribution generated when the dimers (or trimers) are placed near the two electrodes. The electrical conductivity through the system was measured in real time during trapping and also in vacuum after trapping. This enables providing the range for optimum trapping conditions with reasonable current level. The I-V characteristics between dimers and trimers with similar molecular length will be also compared and presented.