(1) Background: The perception of others’ emotions based on non-verbal cues, such as facial expressions, is fundamental for interpersonal communication and mutual support. Using personal protection equipment (PPE) in a work environment during the SAR-CoV-2 pandemic challenged health professionals’ ability to recognise emotions and expressions while wearing PPE. The working hypothesis of this study was that the increased limitation of facial visibility, due to the use of a personal protective device, would interfere with the perception of basic emotions in the participants. (2) Methods: Through a cross-sectional descriptive study, the present research aimed to analyse the identification of four basic emotions (happiness; sadness; fear/surprise; and disgust/anger) through three types of PPE (FFP2 respirator, protective overall and powered air-purifying respirator (PAPR)), by using 32 photographs. The study was conducted using volunteer participants who met the inclusion criteria (individuals older than 13 without cognitive limitations). Participants had to recognise the emotions of actors in photographs that were randomly displayed in an online form. (3) Results: In general, the 690 participants better recognised happiness and fear, independently of the PPE utilised. Women could better identify different emotions, along with university graduates and young and middle-aged adults. Emotional identification was at its worst when the participants wore protective overalls (5.42 ± 1.22), followed by the PAPR (5.83 ± 1.38); the best scores were obtained using the FFP2 masks (6.57 ± 1.20). Sadness was the least recognised emotion, regardless of age. (4) Conclusions: The personal protective devices interfere in the recognition of emotions, with the protective overalls having the greatest impact, and the FFP2 mask the least. The emotions that were best recognised were happiness and fear/surprise, while the least recognised emotion was sadness. Women were better at identifying emotions, as well as participants with higher education, and young and middle-aged adults. View Full-Text ►▼ Show Figures This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.