Pediatric emergency physicians, pediatric critical care specialists, and pediatric surgeons perform central venous catheterization in many clinical settings. Complications of the procedure are not uncommon and can be fatal. Despite the frequency of application, the evidence-base describing the surface landmarks involved is missing. The aim of the current study was to critically investigate the surface markings of the central venous system in children. The superior vena cava/right atrial (SVC/RA) junction, superior vena cava (SVC) formation, and brachiocephalic vein (BCV) formation were examined independently by two investigators. Three hundred computed tomography (CT) scans collected across multiple centers were categorized by age group into: 0-3 years, 4-7 years, and 8-11 years. Scans with pathology that distorted or obscured the regional anatomy were excluded. The BCV formation was commonly found behind the ipsilateral medial clavicular head throughout childhood. This contrasts with the variable levels of SVC formation, SVC length, and SVC/RA junction. In the youngest group, SVC formation was most commonly at the second costal cartilage (CC), but moved to the first CC/first intercostal space (ICS) as the child grew. The SVC/RA junction was at the fourth CC in the youngest group and moved to the third CC/third ICS as the child grew. This study demonstrates the variable anatomy of SVC formation and the SVC/RA junction with respect to rib level. This variability underscores the unreliability of surface anatomical landmarks of the SVC/RA junction as a guide to catheter tip position.