Gas-surface interactions between thermal protection materials and high-enthalpy nonequilibrium flow are one of the greatest challenges in accurately predicting aerodynamic heating during supersonic flights. Finer microscopic details of flow properties are required for elaborate simulation of these interactions. Spectral insight, with quantum-state-specific characteristics, is provided in this work to investigate the physico-chemical processes in high temperature interface of a carbon/carbon (C/C) composite. The nonequilibrium air flow is produced by a 1.2 MW inductively coupled plasma wind tunnel at an enthalpy of 20.08 MJ/kg. The duration of each test is up to 100s, and quartz is also tested for comparison. Spectral insights into the reaction mechanisms of the gas-surface interactions are acquired by the optical emission spectroscopy and laser absorption spectroscopy. Dynamic evolution of the chemical reaction pathways and thermal nonequilibrium are discussed based on the results of optical emission spectroscopy. Temporally and spatially resolved results of the translational temperature and number density of atomic oxygen are quantified by laser absorption spectroscopy. Controlling mechanisms in the surface chemistry are further analyzed in conjunction with the surface temperature, scanning electron microscopy, and energy dispersive spectroscopy. Reaction mechanisms on the C/C composite surface sequentially experience an oxidation-dominant, an intense competitive, a nitridation-dominant, and a recession dominant period. Distributions in the axial direction and dynamic characteristics of the translational temperature and number density of atomic oxygen are found closely related with surface swelling, recession, and chemical reactions. The results herein are consistent with each other and are instructive to further investigate the interface evolution on C/C composites.