The comprehensive evaluation of kV selection on photon-counting computed tomography (PCCT) has yet to be performed. The aim of the study is to evaluate and determine the optimal kV options for variable pediatric body sizes on the PCCT unit. In this study, 4 phantoms of variable sizes were utilized to represent abdomens of newborn, 5-year-old, 10-year-old, and adult-sized pediatric patients. One solid water and 4 solid iodine inserts with known concentrations (2, 5, 10, and 15 mg I/mL) were inserted into phantoms. Each phantom setting was scanned on a PCCT system (Siemens Alpha) with 4 kV options (70 and 90 kV under Quantum Mode, 120 and 140 kV under QuantumPlus Mode) and clinical dual-source (3.0 pitch) protocol. For each phantom setting, radiation dose (CTDIvol) was determined by clinical dose settings and matched for all kV acquisitions. Sixty percent clinical dose images were also acquired. Reconstruction was matched across all acquisitions using Qr40 kernel and QIR level 3. Virtual monoenergetic images (VMIs) between 40 and 80 keV with 10 keV interval were generated on the scanner. Low-energy and high-energy images were reconstructed from each scan and subsequently used to generate an iodine map (IM) using an image-based 2-material decomposition method. Image noise of VMIs from each kV acquisition was calculated and compared between kV options. Absolute percent error (APE) of iodine CT number accuracy in VMIs was calculated and compared. Root mean square error (RMSE) and bias of iodine quantification from IMs were compared across kV options. At the newborn size and 50 keV VMI, noise is lower at low kV acquisitions (70 kV: 10.5 HU, 90 kV: 10.4 HU), compared with high kV acquisitions (120 kV: 13.8 HU, 140 kV: 13.9 HU). At the newborn size and 70 keV VMI, the image noise from different kV options is comparable (9.4 HU for 70 kV, 8.9 HU for 90 kV, 9.7 HU for 120 kV, 10.2 HU for 140 kV). For APE of VMI, high kV (120 or 140 kV) performed overall better than low kV (70 or 90 kV). At the 5-year-old size, APE of 90 kV (median: 3.6%) is significantly higher (P < 0.001, Kruskal-Wallis rank sum test with Bonferroni correction) than 140 kV (median: 1.6%). At adult size, APE of 70 kV (median: 18.0%) is significantly higher (P < 0.0001, Kruskal-Wallis rank sum test with Bonferroni correction) than 120 kV (median: 1.4%) or 140 kV (median: 0.8%). The high kV also demonstrated lower RMSE and bias than the low kV across all controlled conditions. At 10-year-old size, RMSE and bias of 120 kV are 1.4 and 0.2 mg I/mL, whereas those from 70 kV are 1.9 and 0.8 mg I/mL. The high kV options (120 or 140 kV) on the PCCT unit demonstrated overall better performance than the low kV options (70 or 90 kV), in terms of image quality of VMIs and IMs. Our results recommend the use of high kV for general body imaging on the PCCT.