The increase in Australian Human Immunodeficiency Virus (HIV) infections since the 1990s is considered to be due to a subgroup of MSM (men who have sex with men) who engage in behaviors that increase the risk of sexual transmission of HIV. A population of MSM at risk are those who present for PEP (Post-Exposure Prophylaxis). In this article, data from a sample of N = 23 MSM who repeatedly attended an Australian PEP program and sought psychological assistance regarding sexual risk taking are examined. Findings revealed the current sample had more sexual risk behaviors than those of the wider MSM population and had higher Sexual Compulsivity (SC) and Sexual Sensation Seeking (SSSS) scores than previous samples of gay men, along with the finding that SC and SSSS were positively associated with sexual risk taking. Unfortunately, sexual behavior syndromes may be resistant to change, leaving affected MSM at ongoing risk of HIV. If these data can be replicated with larger samples, they point to the value of offering psychological care to affected PEP recipients, and to the role PreP (Pre-Exposure Prophylaxis) may play in providing a safety net against transmission until behavior change occurs.