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Background: Personal protective equipment (PPE) protects healthcare workers and patients. Data on guideline compliance on how to dress (donning) or remove (doffing) PPE and the assistance among multiple participants (buddying) are limited. This study assesses the quality of donning, doffing, and buddying of PPE in a simulated medical emergency. Method: Physicians handling a simulated cardiac arrest of a COVID-19 patient. Adjacent to the victim, PPE was available. The appropriateness of PPE choice was assessed by using video recordings, with each individual participant being analyzed from the beginning of the simulation scenario from two perspectives regarding the selection of items during donning and doffing, hygiene aspects, time, and team support (buddying). The primary outcome was the number of participants being appropriately protected, defined as both wearing (a) all PPE items provided, and (b) all PPE items correctly at the time of first patient contact (FPC). Secondary outcomes included the timing of participants being appropriately protected. Statistical analysis was performed using SPSS (version 28). Mann–Whitney test, chi-square test, and linear regression analysis were performed as appropriate. Results: At first patient contact 21% (91/437) were correctly protected. One or more incorrect PPE items were found in 4% (19/437), whereas 61% (265/437) wore one or more PPE items incorrectly. In 14% (62/437), one or more PPE items were missing. The time interval between donning start and FPC was 66 (55–78) sec. Time to FPC was longer in correctly than in incorrectly protected participants 77 (66–87) vs. 64 (54–75) sec; p < 0.001) and decreased by 7 ± 2 s per PPE item omitted (P = 0.002). Correct doffing was observed in 192/345 (56%), while buddying occurred in 120 participants (27%), indicating that they either assisted other participants in some manner (verbally or physically) or received assistance themselves. Conclusions: Our findings imply a need for education in correct and timely PPE donning and doffing. Donning PPE as intended delayed FPC. This and the influence of buddying needs further investigation (German study register number DRKS00023184). [ABSTRACT FROM AUTHOR]