When does the brain know that a decision is difficult to make? How does decision difficulty affect the allocation of neural resources and timing of constituent cortical processing? Here, we use single-trial analysis of electroencephalography (EEG) to identify neural correlates of decision difficulty and relate these to neural correlates of decision accuracy. Using a cued paradigm, we show that we can identify a component in the EEG that reflects the inherent task difficulty and not simply a correlation with the stimulus. We find that this decision difficulty component arises ≈220 ms after stimulus presentation, between two EEG components that are predictive of decision accuracy [an “early” (170 ms) and a “late” (≈300 ms) component]. We use these results to develop a timing diagram for perceptual decision making and relate the component activities to parameters of a diffusion model for decision making.