For more than 15 years, physicists (and chemists) have been able to perform experimental studies of electronic transport through single molecules in nanoscale junctions, looking at current as a function of voltage. These studies have revealed rich physics, including evidence for quantum entanglement (the Kondo effect) and inelastic processes involving vibrations. However, there are limits to how much one can learn from dc conduction. Fortunately, we have found that some of the same nanoscale metal structures used to perform the electronic measurements have tremendous utility in optical studies. Thanks to plasmons, the collective modes of the electronic fluid, these metal structures act like an optical antenna, channeling optical energy into and out of precisely the region of interest. I will discuss how combining electronic and optical measurements lets us quantify these antenna effects, which allow us to perform Raman spectroscopy with single-molecule sensitivity. I will also show recent results using this spectroscopy to take the effective temperature of both molecular vibrational modes and the electrons in the metal, as current is driven through the junction. This permits new fundamental studies of heating and dissipation at the nanometer scale.