The objectives of the current study were twofold: (i) to investigate the neural precursors of the formation of a subjective preference of facial stimuli, and (ii) to characterize the spatiotemporal brain activity patterns distinguishing between preferred and non-preferred faces. Multivariate EEG signals were recorded while participants made preference decisions, based on approachability, between two faces presented sequentially with unrestricted viewing time; the decision being made after presentation of the second face. The paired faces were similar in their physical properties, emphasizing the role of the subjective experience of the participants in making the decisions. EEG signals were analyzed in terms of event-related-potential (ERP) components and wavelet-based time-frequency-representations (TFR). The behavioural data showed that the presentation order and the exposure duration did not influence preference formation. The EEG data showed three effects. The earliest effect, the sustained posterior ERP positivity for preferred first faces as compared to non-preferred first faces, was found following the onset of the first face, and this was interpreted as the formation of a positive first impression of the first face. The two later effects following the second faces were an increase of frontal theta band oscillations around 500 ms for preferred second faces and of posterior gamma band oscillations around 650 ms for preferred first faces; both of which were interpreted as being related to the formation of a preference. All of these effects occurred well before the moment of conscious decision, thereby suggesting the implicitness of these neurally identifiable components.