Introduction: Appropriate understanding and adherence to antiretroviral regimens are important requisites to the presentation of good outcomes in the Prevention of Mother-to-Child Transmission (PMTCT) of HIV/AIDS. Objectives: This study aimed to evaluate the understanding and level of adherence to antiretroviral regimens among HIV-infected pregnant women. The factors that affect the level were also determined. Methods: Questionnaire was used to measure the knowledge while a modified Morisky Medication Adherence Scale (MMAS-8) and formula were used prospectively to determine their adherence level and the contributing factors. Data were analyzed using statistical products and services solution version 20. Chi-square test was conducted to determine the relationship between factors that affected knowledge and its level while logistic regression was used to determine the predictors of adherence. Results: A total of 394 women participated in the study, out of which 353 (89.6%) women had a good understanding of their PMTCT regimen, which was not affected by their educational levels. They had a low level of adherence among 301(76.4%) respondents. The adherence was not related to their knowledge score. Forgetfulness was a statistically significant (p<0.001) barrier to adherence, as availability of support groups and the understanding of the effectiveness of the regimen, were strong motivators to adherence at p = 0.011 and p = 0.003 respectively. Conclusion: This study concludes that there is a good level of understanding of but the suboptimal level of adherence to PMTCT regimens among the HIV-infected pregnant women in Enugu State, Nigeria.