Understanding and controlling the flow of heat is a major challenge in nanoelectronics. When a junction is driven out of equilibrium by light or the flow of electric charge, the vibrational and electronic degrees of freedom are, in general, no longer described by a single temperature(1-6). Moreover, characterizing the steady-state vibrational and electronic distributions in situ is extremely challenging. Here, we show that surface-enhanced Raman emission may be used to determine the effective temperatures for both the vibrational modes and the electrons in the current in a biased metallic nanoscale junction decorated with molecules(7). Molecular vibrations show mode-specific pumping by both optical excitation(8) and d.c. current(9), with effective temperatures exceeding several hundred kelvin. Anti-Stokes electronic Raman emission(10,11) indicates that the effective electronic temperature at bias voltages of a few hundred millivolts can reach values up to three times the values measured when there is no current. The precise effective temperatures are model-dependent, but the trends as a function of bias conditions are robust, and allow direct comparisons with theories of nanoscale heating.