The aim of this study was to use near-infrared time-resolved spectroscopy (TRS) to determine the absolute values of cerebral blood volume (CBV) and cerebral hemoglobin oxygen saturation (ScO2) during the immediate transition period in term neonates and the changes in optical properties such as the differential pathlength factor (DPF) and reduced scattering coefficient (μs’). CBV and ScO2 were measured using TRS during the first 15 min after birth by vaginal delivery in term neonates who did not need resuscitation. Within 2–3 min after birth, CBV showed various changes such as increases or decreases, followed by a gradual decrease until 15 min and then stability (mean (SD) mL/100 g brain: 2 min, 3.09 (0.74); 3 min, 3.01 (0.77); 5 min, 2.69 (0.77); 10 min, 2.40 (0.61), 15 min, 2.08 (0.47)). ScO2 showed a gradual increase, then kept increasing or became a stable reading. The DPF and μs’ values (mean (SD) at 762, 800, and 836 nm) were stable during the first 15 min after birth (DPF: 4.47 (0.38), 4.41 (0.32), and 4.06 (0.28)/cm; μs’: 6.54 (0.67), 5.82 (0.84), and 5.43 (0.95)/cm). Accordingly, we proved that TRS can stably measure cerebral hemodynamics, despite the dramatic physiological changes occurring at this time in the labor room.