Vaccines are among the most successful and cost-effective public health tools and have greatly contributed to eliminating or controlling several serious vaccine-treatable diseases over the past century. To curb the spread of COVID-19, efficacious vaccination is emerging as essential in mitigating the disease and preventing deaths. Health care workers (HCW) are one of the first groups to receive vaccinations, so it is important to consider their attitudes to COVID-19 vaccination to better address barriers to widespread vaccination acceptance. This study aimed to evaluate variables that are linked with the recommendation of vaccines and intention to take-up vaccination against COVID-19 among the HCWs, in the context of the current pandemic. The study was conducted during the first week of the vaccination campaign dedicated to Italian HCWs, beginning in December 2020, and it involved all doctors in a public hospital in Sicily. The following questionnaires were administered: (1) The perceived vaccine trust questionnaire, measuring the degree of trust in vaccines by healthcare professionals both in general and for the protection of healthcare professionals themselves and patients; (2) the positive and negative affect scale-state (PANAS), for assessing positive and negative emotions in relation to their work as “frontline care providers”; (3) The locus of control of behaviour (LCB) to measure the extent to which subjects perceive responsibility for their personal behaviour (internal vs. external); (4) recommendation vaccines item, referring to the intention to recommend vaccination. The findings suggest that socio-demographic control variables (age, gender, and seniority) showed little or no predictive power in vaccine recommendation, while vaccine confidence, positive emotions, and internal locus of control were excellent predictors of vaccine recommendations by doctors. Younger doctors, both in age and experience, are more confident in vaccines and recommend them more frequently. It is essential to improve institutional communication addressed to doctors to enhance their role as vaccination facilitators.