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One of the first alternative fuels have been fossil crude oil based containing a small amount of biomass derived compounds (bioethanol or biodiesel). Biofuels usually contain oxygenated hydrocarbons such as alcohols or esters. The increasing use of alternative fuels will occur at the same time when various after-treatment systems (oxidation catalysts, filters, SCR catalysts) will be commercialized world-widely between 2010 and 2020. The effects of biofuels on emissions and emission catalysts were reviewed widely in this study. The change in raw emissions has effects on the selection, performance and durability of catalytic systems. Bioethanol has been used widely with emission catalysts since 1990's in Brazil. The results with three-way catalysts (TWC) were analyzed in those conditions. PtRh catalysts showed the better performance and durability than Pd containing TWCs.