This paper reports on the influence that extreme values in the tails of the North Atlantic Oscillation (NAO) Index probability density function (PDF) can exert on temperatures in Europe.When the NAO Index enters into its lowest (10% quantile or less) and highest (90% quantile or higher) modes, European temperatures often exhibit large negative or positive departures from their mean values, respectively. Analyses of the joint quantiles of the Index and temperatures (i.e., the simultaneous exceedance of particular quantile thresholds by the two variables) show that temperatures enter into the upper or lower tails of their PDF when the NAO Index also enters into its extreme tails, more often that could be expected from random statistics. Studies of this nature help further our understanding of the manner by which mechanisms of decadal-scale climate variability can influence extremes of temperature—and thus perhaps improve the forecasting of extreme temperatures in weather and climate models.