© 2019 Elsevier B.V. An in-situ temperature-controlled Raman spectroscopy aided unique electrode fabrication technique has been developed for Li-ion battery applications, ensuring superior electrochemical quality of the multi-porous LiCoO2 films with higher stoichiometric purity of high temperature (HT)-LiCoO2 phase, by observing the structural changes during the fabrication process and thus confirming the transformation from the low temperature (LT)-LiCoO2 phase. This much desired simple process is not only free of any sort of binders or carbon additives but also works at atmospheric pressure, leading to a very simple deposition technique using a homemade and inexpensive set-up. Also, the time of depositions were varied and resultant films we investigated for their electrochemical performance. The high-resolution scanning electron microscope (SEM) observation has revealed not only a μm-size porous structure but also three-dimensional cross-link with 10 nm-level pores of the material, which ensured the much-desired porosity for high-performance cathodes.