Although humans are considered to be face experts, there is a well-established reliable variation in the degree to which neurotypical individuals are able to learn and recognise faces. While many behavioural studies have characterised these differences, studies that seek to relate the neuronal response to standardised behavioural measures of ability remain relatively scarce, particularly so for the time-resolved approaches and the early response to face stimuli. In the present study we make use of a relatively recent methodological advance, multi-variate pattern analysis (MVPA), to decode the time course of the neural response to faces compared to other object categories (inverted faces, objects). Importantly, for the first time, we directly relate metrics of this decoding assessed at the individual level to gold-standard measures of behavioural face processing ability assessed in an independent task. Thirty-nine participants completed the behavioural Cambridge Face Memory Test (CFMT), then viewed images of faces and houses (presented upright and inverted) while their neural activity was measured via electroencephalography. Significant decoding of both face orientation and face category were observed in all individual participants. Decoding of face orientation, a marker of more advanced face processing, was earlier and stronger in participants with higher levels of face expertise, while decoding of face category information was earlier but not stronger for individuals with greater face expertise. Taken together these results provide a marker of significant differences in the early neuronal response to faces from around 100ms post stimulus as a function of behavioural expertise with faces.