Objective: This study aimed to (i) capture clinicians' knowledge, attitude and adherence to the first Australian national peripheral intravenous catheter (PIVC) Clinical Care Standard, (ii) examine the instrument performance of the knowledge related questions and (iii) explore the educational needs for, and barriers to, Standard adherence among Australian ED clinicians. Methods: A cross-sectional national online survey was conducted from March to June 2022, using a snowball sampling method. The survey used 5-point Likert scales and multiple-choice questions to capture respondents' knowledge, attitude and adherence to the Standard as well as the educational needs for, and barriers to, Standard adherence. Results: In total, 433 ED nurses and doctors responded. Although nearly half (n = 206, 47.6%; 95% confidence interval [CI] 55.5–65.8) of respondents claimed that they were unfamiliar with the Standard, questions on PIVC knowledge yielded that most respondents had adequate knowledge of most of the key standards. Respondents' attitudes towards multiple intravenous insertion attempts and ongoing PIVC competency monitoring are not in agreement with the Standard. Self-reported practices regarding routine insertion of idle catheters (55%; 95% CI 49.9–59.9), using antecubital fossa as the first insertion site (84%; 95% CI 80–87), insertion without confidence (46%; 95% CI 41.2–51.1) and lack of routine reviewing the ongoing needs of PIVC (40%; 95% CI 35.3–45.1) were not aligned with the Standard. Unawareness of the Standard and non-practical recommendations were rated as the top barriers to Standard adherence. Conclusion: The findings of the survey suggest that the Standard may need modification to align with the needs of ED clinicians. Future studies need to explore the applicability and relevancy of some recommendations in the ED settings as they may cause low adherence to the Standard.