Tracking thermally induced reactions has always been challenging for electrode materials of electrochemical battery systems. Traditionally, a variety of calorimetric techniques and in situ XRD at elevated temperatures has been used to evaluate the thermal stability of electrode materials. These techniques are capable of providing variations in heat capacity, mass and average bulk composition of materials only. Herein, we report investigation of thermal characteristics of Li0.33Ni0.8Co0.15Al0.05O2 by using in situ soft XAS measurements in combination with XRD. Fluorescence yield and partial electron yield measurements are used simultaneously to obtain element selective surface and bulk information. Fluorescence yield measurements reveal no energy change of the absorption peak and thus no valence state change in the bulk. However, electron yield measurements indicate that NiO-type rock salt structure is formed at the surface at temperatures above 200°C while no evidence for a surface reaction near Co sites in investigated temperature range is found. These results clearly show that in situ soft XAS can give a unique understanding of the role of each element in the structural transformation under thermal abuse offering a useful guidance in developing new battery system with improved safety performance.