Introduction Peritoneal dialysis (PD) is an alternative modality to hemodialysis (HD) for end-stage Kidney disease (ESKD) treatment. However, PD is underutilized, and patients’ knowledge about PD is crucial in making an informed decision about the dialysis modality. This study aims to evaluate the knowledge about PD among HD patients and explore the reasons for its underutilization. Materials and methods A cross-sectional study of 108 HD patients was conducted from August to November 2023, at Al-Jaber Dialysis Center in Al-Ahsa. They interviewed to assess the knowledge about PD and explore the reasons for its underutilization. Results The patients’ ages ranged from 20 to 80 years, with a mean age of 44.2 years. Regarding knowledge about PD, 81.5% of the ESKD patients had heard about other renal replacement modalities, with kidney transplant being the most commonly known option. Only 11.1% were aware of both kidney transplants and PD. 60.2% of patients reported that their nephrologists had discussed other treatment options with them. However, overall knowledge about PD among patients was relatively low, with 43.5% having good knowledge and 56.5% having poor knowledge. Lack of information, considering HD as a better method, and fear of complications were the primary reasons for not considering PD as the first treatment option. Conclusion This study highlights the inadequate knowledge about PD among HD patients and identifies factors contributing to the underutilization of PD. Lack of information, misconceptions about the effectiveness and safety of PD, and preference for HD were significant barriers. Enhancing patient education and addressing misconceptions are crucial in promoting PD as a viable treatment option for ESKD, thereby improving patients’ quality of life.