Background: Prisoners have poorer dental health than non-prison populations. It is known that the prison environment can promote health and thus, policies, including access to dental care, are in place to promote health during imprisonment. Aim: Our aim was to conduct an oral health and psychosocial needs survey to identify the factors associated with accessing prison dental services in Scotland. Methods: A convenience sample of offenders from a male maximum security prison, a women’s prison, and a young offenders’ institution was gathered. A questionnaire examined the demography, prison experience, dental anxiety, oral health-related quality of life, and reported attendance of dental services. A dental examination was conducted using the International Caries Detection and Assessment System to diagnose obvious decay. A hierarchical logistic regression analysis was performed. Results: 342 prisoners participated. When missing data were excluded, the final sample was 259. The regression analysis showed the following: Model 1 characterized the offenders by demography and prison experience, explaining 19% of the variance. Model 2 showed that an offender was 36% more likely to attend dental services for every unit change in the 5-point ranking scale of ‘feeling irritable with people because of teeth, mouth, or dentures’, explaining an additional 7% of the variance. Model 3 explained 35% of the variance, (i.e., an additional 9%) and was adopted as the final model to characterize offenders who access dental services when in prison. An offender who reported accessing prison dental services was 3.28 times more likely to be male. For each increase in the year of an offender’s age, the offender was 5% more likely to access prison dental services. An 11% greater chance of accessing prison dental services for every experience of remand was also found. An offender was 32% more likely to access prison dental services for each increased level of irritability, and there was a 2 times higher likelihood of emergency dental services’ attendance. There was a 19% lower chance of accessing prison dental services for each additional tooth affected by decay and a 13% greater chance of accessing prison dental services for each unit increase in missing teeth. Conclusions: In conclusion, this investigation identified factors associated with access to prison dental services in Scotland. The role of accessibility factors, such as the oral health impact of irritability, appeared to increase perceptions of dental need and promote dental services’ attendance.