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XRD pattern of β-Ga2O3 powder, synthesized through template-free two step hydrothermal method at low temperature thoroughly, is investigated by imposing different methods of analysis. Both crystallite sizes and micro-strains of the micro-structures are analyzed and compared. Along with the traditional Scherrer’s formula (S-average, LF and LFTZ), modified Williamson–Hall (W-H) method with UDM, USDM and UDEDM and Size-Strain Plot (SSP) method were used for the investigation. Stress and defect energy densities were calculated from USDM and UDEDM modified W-H plots of the powder sample, respectively. Detailed analysis of the crystallite size and micro-strain from different methods/models was done. Obtained crystallite sizes and micro-strains from different models were compared with the results obtained from TEM analysis. It was found that crystallite sizes obtained from UDM modified W-H analysis and SSP models well coincided with crystallite size observed from TEM micrograph.