The Centers for Disease Control and Prevention (CDC) and the World Health Organization (WHO) have established guidelines for HIV testing in healthcare settings. The aim of this study was to identify the sociodemographic, healthcare, and sexual-behavior predictors of provider-initiated HIV testing (PIHT) using data from the Puerto Rico National HIV Behavioral Surveillance (PR-NHBS) 2016 cycle directed towards heterosexuals at increased risk of HIV infection (HET). A total sample of 531 eligible participants were recruited through respondent-driven sampling (RDS). Logistic regression models assessed the associations between sociodemographic, healthcare, and sexual-behavior predictors, whilst adjusting for sex and age. The majority of the participants were women (66.1%), with 72.7% reporting having received healthcare services in the past year. Of them, 18.7% had received an HIV-test offer from their healthcare providers. More than half of the participants (65.2%) reported a low perceived risk of getting infected with HIV in the next 12 months. Results suggest an overall low prevalence of PIHT among HET in PR who exhibited a relatively high prevalence of low perceived risk of HIV infection. Furthermore, the assessed predictors show that individuals who engaged in high-risk sexual behaviors (AOR = 0.52; 95% CI: 0.30–0.90) were less likely to receive HIV-test offers from their providers. This study further emphasizes the need for healthcare providers to follow recommended guidelines for HIV testing in healthcare settings as a means of establishing preventive measures to further counteract the HIV epidemic in Puerto Rico, specifically among HET.