Quantitative understanding of 2D atomic layer interface thermal resistance (R) based on Raman characterization is significantly hindered by unknown sample-to-sample optical properties variation, interface-induced optical interference, off-normal laser irradiation, and large thermal-Raman calibration uncertainties. In this work, we develop a novel energy transport state resolved Raman (ET-Raman) to resolve these critical issues, and also consider the hot carrier diffusion, which is crucial but has been rarely considered during interface energy transport study. In ET-Raman, by constructing two steady heat conduction states with different laser spot sizes, we differentiate the effect of R and hot carrier diffusion coefficient (D). By constructing an extreme state of zero/negligible heat conduction using a picosecond laser, we differentiate the effect of R and material's specific heat. In the end, we precisely determine R and D without need of laser absorption and temperature rise of the 2D atomic layer. Seven MoS 2 samples (6.6−17.4 nm) on c-Si are characterized using ET-Raman. Their D is measured in the order of 1.0 cm 2 /s, increasing against the MoS 2 thickness. This is attributed to the weaker in-plane electron−phonon interaction in thicker samples, enhanced screening of long-range disorder, and improved charge impurities mitigation. R is determined as 1.22−1.87 × 10 −7 K•m 2 /W, decreasing with the MoS 2 thickness. This is explained by the interface spacing variation due to thermal expansion mismatch between MoS 2 and Si, and increased stiffness of thicker MoS 2 . The local interface spacing is uncovered by comparing the theoretical Raman intensity and experimental data, and is correlated with the observed R variation.