(1) Background: Human papillomavirus (HPV) infection is significantly associated with oropharyngeal squamous cell carcinoma (HPV-OPSCC), which is one of the fastest-growing cancer incidences globally. Dental practitioners play a crucial role in the primary and secondary prevention of HPV-OPSCC. There is little known about dental students’ awareness regarding HPV-OPSCC and HPV vaccination, as well as their intention to promote ‘primordial prevention’ among their patients. HPV vaccine, and the extent of their professional responsibilities. (2) Methods: This cross-sectional study was conducted in the western region of Saudi Arabia and involved undergraduate dental students (n = 688) from six public and private dental schools. Participants were requested to complete a sequential-section anonymous online survey, with 257 successfully completing all sections of the questionnaire. The association between participant characteristics and HPV-OPSCC, HPV vaccination awareness ratings, and perceived engagement in prevention were analyzed using ANOVA and chi-squared testing. A binary logistic regression analysis was conducted to examine the variables linked to these outcomes. (3) Results: Generally, the overall level of awareness of HPV-OPSCC and HPV vaccination was acceptable, with an average score of 53.44 ± 29.3 out of 100. However, a significant knowledge gap was observed, with 53% of respondents being unaware of the common sites for HPV-OPSCC and 63.8% being uninformed of the appropriate age for HPV vaccination. Females and those with a prior history of sexually transmitted diseases (STDs) had considerably higher levels of HPV vaccination knowledge (p < 0.05). The participants showed a favorable attitude towards their responsibility of informing patients about HPV-OPSCC and advocating HPV immunization. (4) Conclusions: This study underscores the need to enhance dental students’ understanding of HPV-OPSCC and HPV immunization, enabling them to effectively engage in primary and secondary preventative efforts against HPV-OPSCC.