Advanced biofuels and electrofuels, among which are medium-long chain alcohols, have gained importance in the transport sector with the enforcement of the EU Renewable Energy Directive (2018/2001). In parallel, last European emission regulations have become much more restrictive regarding NOx, so vehicle manufacturers have been forced to incorporate lean NOx trap (LNT) and/or selective catalytic reduction (SCR). Thus, the combination of modern DeNOx devices and the upcoming higher contribution of sustainable biofuels is a new challenge. In this work, two Euro 6 diesel vehicles, one equipped with LNT and the other with ammonia-SCR, have been tested following the Worldwide harmonized Light-duty vehicles Test Cycle (WLTC) at warm (24°C) and cold (−7°C) conditions using conventional diesel fuel and a diesel-butanol (90/10% vol.) blend. While the effect of butanol on the LNT efficiency was not significant, its influence on the SCR performance was notable during the low and medium-speed phases of the driving cycle, mainly under warm climatic conditions. Despite of the lower NOx concentration at the catalyst inlet, the worst efficiency of the SCR with butanol could be attributed to hydrocarbons deposition on the catalyst surface, which inhibits the NOx reduction reactions with ammonia. Moreover, the LNT was not sensitive to the ambient temperature while the SCR performance greatly depended on this parameter.