The physics and chemistry of a charged interface are governed by the structure of the electrical double layer (EDL). Determination of the interfacial water thickness (diw) of the charged interface is crucial to quantitatively describe the EDL structure, but it can be utilized with very scarce experimental methods. Here, we propose and verify that the vibrational relaxation time (T1) of the OH stretching mode at 3200 cm-1, obtained by time-resolved sum frequency generation vibrational spectroscopy with ssp polarizations, provides an effective tool to determine diw. By investigating the T1 values at the SiO2/NaCl solution interface, we established a time-space (T1-diw) relationship. We find that water has a T1 lifetime of ≥0.5 ps for diw ≤ 3 Å, while it displays bulk-like dynamics with T1 ≤ 0.2 ps for diw ≥ 9 Å. T1 decreases as diw increases from ∼3 Å to 9 Å. The hydration water at the DPPG lipid bilayer and LK15β protein interfaces has a thickness of ≥9 Å and shows a bulk-like feature. The time-space relationship will provide a novel tool to pattern the interfacial topography and heterogeneity in Ångstrom-depth resolution by imaging the T1 values.