The interpretation of emotional facial expressions is crucial in everyday social interactions, and rapid processing of these expressions is necessary. Although extensive research has shed light on the mechanisms involved in facial expression processing, there is limited research on the potential role of the state of neural activity that directly precedes the occurrence of a face. Here, we investigated the potential modulatory role of pre-stimulus oscillatory activity in emotional facial expression processing. We tested emotional facial processing in two experiments, one utilizing artificial and the other natural facial expressions. The participants had to evaluate the emotional valence of the presented ambiguous facial expressions. In a univariate analysis, differences in the oscillation activity of the later rated valence of the faces were observed in both experiments, and these differences were observed even before the presentation of the facial expressions. Importantly, two different multivariate approaches directly supported the relevance of pre-stimulus oscillatory activity by exclusively using pre-stimulus oscillatory data to predict the perceived valence of the latter rated facial expression across the two experiments within as well as across subjects. The behavioral data shows the often observed negativity bias, i.e. ambiguous faces resulted in the tendency to rate them as negative. This negativity bias was related to neural activity modulations in the pre-stimulus period and also within post-stimulus processing related activity. These findings underscore the significance of pre-stimulus oscillatory activity in facial expression processing, indicating a functional role of ongoing neural states that affects the processing of facial expressions and constitute a basis for the well described negativity bias.