Perceptually similar stimuli, despite not being consciously distinguishable, may result in distinct cortical brain activations. Hypothesizing that perceptually similar tastes are discriminable by electroencephalography (EEG), we recorded 22 human participants’ response to equally intense sweet-tasting stimuli: caloric sucrose, low-caloric aspartame, and a low-caloric mixture of aspartame and acesulfame K. Time-resolved multivariate pattern analysis of the 128-channel EEG was used to discriminate the taste responses at single-trial level. Supplementing the EEG study, we also performed a behavioral study to assess the participants’ perceptual ability to discriminate the taste stimuli by a triangle test of all three taste pair combinations. The three taste stimuli were found to be perceptually similar or identical in the behavioral study, yet discriminable from 0.08 to 0.18 s by EEG analysis. Comparing the participants’ responses in the EEG and behavioral study, we found that brain responses to perceptually similar tastes are discriminable, and we also found evidence suggesting that perceptually identical tastes are discriminable by the brain. Moreover, discriminability of brain responses was related to individual participants’ perceptual ability to discriminate the tastes. We did not observe a relation between brain response discriminability and calorie content of the taste stimuli. Thus, besides demonstrating discriminability of perceptually similar and identical tastes with EEG, we also provide the first proof of a functional relation between brain response and perception of taste stimuli at individual level.