Some evidence suggests that experiencing a given scenario using virtual reality (VR) may engage greater attentional resources than experiencing the same scenario on a 2D computer monitor. However, the underlying neural processes associated with these VR-related effects, especially those pertaining to current consumer-friendly head-mounted displays of virtual reality (HMD-VR), remain unclear. Here, two experiments were conducted to compare task performance and EEG-based neural metrics captured during a perceptual discrimination task presented on two different viewing platforms. Forty participants (20–25 years old) completed this task using both an HMD-VR and traditional computer monitor in a within-group, randomized design. Although Experiment I (n = 20) was solely behavioral in design, Experiment II (n = 20) utilized combined EEG recordings to interrogate the neural correlates underlying potential performance differences across platforms. These experiments revealed that (1) there was no significant difference in the amount of arousal measured between platforms and (2) selective attention abilities in HMD-VR environment were enhanced from both a behavioral and neural perspective. These findings suggest that the allocation of attentional resources in HMD-VR may be superior to approaches more typically used to assess these abilities (e.g., desktop/laptop/tablet computers with 2D screens).