Purpose: To identify and understand the multifaceted barriers faced by Syrian refugees when seeking vaccination services for their children. Methods: A survey questionnaire was administered through structured interviews to a sample of Syrian refugees residing inside the Al-Zaatari camp and in various urban areas across Jordanian communities. This process utilized a multi-stage sampling approach, beginning with a random selection from clusters or strata, and then employing convenience sampling within each to select participants. The survey covered demographics, barriers to vaccination, and vaccine hesitancy. Results: A total of 332 participants completed the survey with a mean age of 32.7 ± 10 years ranging from 18 to 67. More than half of the sample (59%) had an education of 11th grade or less. Sociodemographic disparities regarding barrier perception were evident among participants. Middle-aged adults (older than 32), males, and those with a monthly income less than USD 200 had scored significantly higher on barrier perceptions across all categories (p < 0.05). In-camp residents were less likely to face vaccination barriers compared to those living outside the camps (p < 0.001). Psychological antecedents of vaccine assessments showed that younger individuals had significantly higher scores in complacency, calculation, and constraints (p < 0.05). Participants with lower income had lower constraints and calculation scores (p < 0.05). In-camp residents had significantly higher scores in complacency, constraints, and calculation constructs compared outside camps counterparts (p < 0.05). Participants with no formal education had higher scores in complacency and constraints, and those with less than a 12th-grade education and higher education degrees scored significantly higher on the collective responsibility construct (p < 0.05). Conclusions: Efforts to promote vaccination among refugees should consider the specific challenges faced by this population, including financial barriers, healthcare access inequalities, and the impact of living arrangements. Public health strategies should address not only individual and psychological factors but also the physical and logistical challenges in obtaining vaccines.