Improvements are made to existing primitive cell volume measurement method to provide a real-time analysis capability for the phase analysis of nanocrystalline materials. Simplification is introduced in the primitive cell volume calculation leading to fast and reliable method for nano-phase identification and is applied to the phase analysis of Mo-Si-N nanocoating layer. In addition, comparison is made between real-time and film measurements for their accuracy of calculated primitive cell volume values and factors governing the accuracy of the method are determined. About 5% accuracy in primitive cell determination is obtained from camera length calibration and this technique is used to investigate the cell volume variation in WC-TiC core-shell microstructure. In addition to chemical compositional variation in core-shell type structure, primitive cell volume variation reveals additional information on lattice coherency strain across the interface.