In order to combat the threat of climate change, countries have begun to implement policies which restrict GHG emissions in the electricity sector. However, the development of national electricity mixes should also be sensitive to resource availability, geo-political forces, human health impacts, and social equity concerns. Policy focused on GHG goals could potentially lead to adverse consequences in other areas. To explore the impact of "climate-centric" policy making on long-term electricity mix changes, we develop two cases for Peru and Spain analyzing their changing electricity grids in the period 1989-2013. We perform a Life Cycle Assessment of annual electricity production to catalogue the improvements in GHG emissions relative to other environmental impacts. We conclude that policies targeting GHG reductions might have the co-benefit of also reducing air pollution and toxicity at the expense of other important environmental performance indicators such as water depletion. Moreover, as of 2013, both countries generate approximately equal GHG emissions per kWh, and relatively low emission rates of other pollutants compared to nations of similar development levels. Although climate-centric policy can lead to some positive environmental outcomes in certain areas, energy policy-making should be holistic and include other aspects of sustainability and vulnerability.