Pairs of emotional (pleasant or unpleasant) and neutral scenes were presented peripherally (5 degrees away from fixation) during a central letter-discrimination task. Selective attentional capture was assessed by means of eye movement orienting, i.e., probability of first fixating a scene and the time until first fixation. Static and dynamic visual saliency values of the scenes were computationally modelled. Results revealed selective orienting to both pleasant and unpleasant relative to neutral scenes. Importantly, such effects remained in the absence of visual saliency differences, even though saliency influenced eye movements. This suggests that selective attention to emotional scenes is genuinely driven by the processing of affective significance in extrafoveal vision.