The aim of this study was to capture Australian frontline healthcare workers’ (HCWs) experiences with personal protective equipment (PPE) during the COVID-19 pandemic in 2020. This was a cross-sectional study using an online survey consisting of five domains: demographics; self-assessment of COVID risk; PPE access; PPE training and confidence; and anxiety. Participants were recruited from community and hospital healthcare settings in Australia, including doctors, nurses, allied health professionals, paramedics, and aged care and support staff. Data analysis was descriptive with free-text responses analysed using qualitative content analysis and multivariable analysis performed for predictors of confidence, bullying, staff furlough and anxiety. The 2258 respondents, comprised 80% women, 49% doctors and 40% nurses, based in hospital (39%) or community (57%) settings. Key findings indicated a lack of PPE training (20%), calls for fit testing, insufficient PPE (25%), reuse or extended use of PPE (47%); confusion about changing guidelines (48%) and workplace bullying over PPE (77%). An absence of in-person workplace PPE training was associated with lower confidence in using PPE (OR 0.21, 95%CI 0.12, 0.37) and a higher likelihood of workplace bullying (OR 1.43; 95% CI 1.00, 2.03) perhaps reflecting deficiencies in workplace culture. Deficiencies in PPE availability, access and training linking to workplace bullying, can have negative physical and psychological impacts on a female dominant workforce critical to business as usual operations and pandemic response.