This study mainly explored the behavioral intention and influencing factors of medical staff toward COVID-19 vaccinations. Medical staff were taken as the research subjects. This study selected 300 research subjects by the intentional sampling method and conducted a questionnaire survey. A total of 260 questionnaires were recovered (a recovery rate of 86%), and the number of valid questionnaires was 212, for an effective questionnaire rate of 81%. SPSS and AMOS were used for statistical analysis. As known from the research results: (1) medical staffs’ perception of COVID-19 vaccinations had a positive and significant impact on their behavioral intention for receiving COVID-19 vaccinations; (2) medical staffs’ perception of COVID-19 vaccinations had a negative and significant impact on the barriers to receiving COVID-19 vaccinations; (3) medical staffs’ motivation of receiving COVID-19 vaccinations had a positive and significant positive effect on their behavioral intention of receiving COVID-19 vaccinations; and (4) medical staffs’ motivation of receiving COVID-19 vaccinations had a positive and significant impact on the barrier to receiving COVID-19 vaccinations.