As the continuance of our series study on LiCoO2 surface modification, the complicated traditional surface coating method is replaced with simple addition of amorphous YPO4 and Al2O3 in commercial LiCoO2 or in commercial electrolyte based on our understanding to the improvement mechanism of surface modification. Comprehensive studies by X-ray photoelectron spectroscopy (XPS), gas chromatography and mass spectroscopy (GC–MS), inductively coupled plasma (ICP) and Fourier transformed infrared (FTIR) indicate that the products of spontaneous reaction between the additive and the LiPF6 based electrolyte are responsible for the performance improvements.