Compared to comparably sized conventional light duty gasoline vehicles (CLDGVs), plug-in hybrid electric vehicles (PHEVs) may offer benefits of improved energy economy, reduced emissions, and the flexibility to use electricity as an energy source. PHEVs operate in either charge depleting (CD) or charge sustaining (CS) mode; the engine has the ability to turn on and off; and the engine can have multiple cold starts. A method is demonstrated for quantifying the real-world activity, energy use, and emissions of PHEVs, taking into account these operational characteristics and differences in electricity generation resource mix. A 2013 Toyota Prius plug-in was measured using a portable emission measurement system. Vehicle specific power (VSP) based modal average energy use and emission rates are inferred to assess trends in energy use and emissions with respect to engine load and for comparisons of engine on versus engine off, and cold start versus hot stabilized running. The results show that, compared to CLDGVs, the PHEV operating in CD mode has improved energy efficiency and lower CO2, CO, HC, NOx, and PM2.5 emission rates for a wide range of power generation fuel mixes. However, PHEV energy use and emission rates are highly variable, with periods of relatively high on-road emission rates related to cold starts.