Single and multi-unit recordings in primates have identified spatially localized neuronal activity correlating with an animal’s behavioral performance. Due to the invasive nature of these experiments, it has been difficult to identify such correlates in humans. We report the first non-invasive neural measurements of perceptual decision making, via single-trial EEG analysis, that lead to neurometric functions predictive of psychophysical performance for a face versus car categorization task. We identified two major discriminating components. The earliest correlating with psychophysical performance was consistent with the well-known face-selective N170. The second component, which was a better match to the psychometric function, did not occur until at least 130 ms later. As evidence for faces versus cars decreased, onset of the later, but not the earlier, component systematically shifted forward in time. In addition, a choice probability analysis indicated strong correlation between the neural responses of the later component and our subjects’ behavioral judgements. These findings demonstrate a temporal evolution of component activity indicative of an evidence accumulation process which begins after early visual perception and has a processing time that depends on the strength of the evidence.