Boron-substituted LiCrO2 battery cathode material samples were investigated by X-ray-based techniques to probe the influence of boron on their crystal and electronic structure properties. Studies were carried on a series of Li-ion battery cathode materials with the general formula LiCr1−xBxO2. Up to 10 pct boron substitution amounts, light boron atoms were determined to sit in Cr coordinations. However, for more substitutions (>10 pct), higher electronegativity of boron was determined to govern the crystal structure by obtaining isolated boron-centered domains and built Li2BO4 structures. Electronic structure studies and further crystal structure analysis were carried by X-ray absorption fine structure technique. In the studied samples, increasing boron concentration in the samples (i.e., >10 pct substitution) were determined to cause a decrease in oxygen bond distances as a result of boron sitting in some chromium locations. As a result of this study, 10 pct boron substitution was determined as a threshold to protect the LiCrO2 crystal structure.