Background: Vascular access (VA) is one of the most critical procedures during dialysis for patients with end-stage renal disease (ESRD), as it influences morbidity, mortality, and quality of life. Methods: This cross-sectional study analyzed the vascular access epidemiology of patients undergoing chronic HD in 15 nephrology centers across Greece from 2013 to 2019. Data on VA type, demographic characteristics, fatigue severity, and quality of life were gathered from a sample of 373 patients. Results: The prevailing result of this study is that arteriovenous fistula (AVF) was the commonly practiced VA, and its associated survival outcomes were better when compared to arteriovenous grafts (AVGs) and central venous catheters (CVCs). Patients with AVFs had significantly longer survival times (median 165 months) compared to non-fistula access. Furthermore, the degree of fatigue and quality of life were also dependent on the type of VA used, with patients on AVF having lower fatigue levels and better quality of life. Age, gender, and an early nephrologist referral were noted to affect the selection and the rate of maturation of VA. Despite AVF being the preferred VA, late referrals and high initial reliance on CVCs remain challenges. Conclusions: This study underscores the need for early nephrological intervention, surveillance programs, and patient education to optimize vascular access outcomes. Future research should focus on national strategies to reduce CVC-related complications and improve long-term HD care in Greece.