The ability to controllably assembly nanoscale building blocks into higher order architectures is crucial for the fabrication of functional materials and devices. Herein, we demonstrate the control of orientation, coordination, and interparticle distance of plasmonic nanoparticles through a polymer-assisted assembly mechanism. By modifying the shape and surface chemistry of the particles we were able to build homo- and hybrid plasmonic nanojunctions which can be used in high-resolution sensing and imaging, as well as enhancement of light absorption in photovoltaics