Microstructure of chemically synthesized wurtzite-type CdS nanocrystals have been investigated by X-ray diffraction (XRD) peak profile analysis by applying different forms of Williamson–Hall (WH) method viz., uniform deformation model (UDM), uniform stress deformation model (USDM) and uniform deformation energy density model (UDEDM), and transmission electron microscope (TEM) observations. The WH methods show the average crystallite size to beabout 10 nm. Strain, stress and energy density of the nanocrystals are found to be $1.18 \times 10^{−2}, 0.43$ GPa and $2.27$ kJ m$^{−3}$, respectively. High-resolution TEM (HRTEM) results show the nanocrystals to be in spherical shape with an average crystallite size of 10 nm, thereby complementing the size estimation by WH methods. Further, HRTEM observations reveal the presence of edge dislocations and twin boundaries within the nanocrystals.