Previous findings of better behavioral responses to self- over other-related stimuli suggest prioritized cognitive processes of self-related information. However, it is unclear whether the processing of information related to important others (e.g.friends) may be prioritized over that related to the self in certain subpopulations and, if yes, whether friend-prioritization and self-prioritization engage distinct cognitive and neural mechanisms. We collected behavioral and electroencephalography (EEG) data from a large sample (N = 1006) during learning associations between shapes and person labels (self or a friend). Analyses of response times and sensitivities revealed two subpopulations who performed better to friend-shape or self-shape associations, respectively (N = 216 for each group). Drift diffusion model (DDM) analyses unraveled faster information acquisition for friend-shape (vs. self-shape) associations in the friend-prioritization group but an opposite pattern in the self-prioritization group. Trial-by-trial regression analyses of EEG data showed that the greater amplitudes of a frontal/central activity at 180-240 ms poststimulus were correlated with faster information acquisition from friend-shape associations in the friend-prioritization group but from self-shape associations in the self-prioritization group. However, the frontal/central neural oscillations at 8-18 Hz during perceptual learning were specifically associated with speed of information acquisition from friend-shape associations in the friend-prioritization-group. Our findings provide evidence for friend-prioritization in perceptual learning in a subpopulation of adults and clarify the underlying cognitive and neural mechanisms.