The absolute doubly differential cross-sections (DDCS) for production of the thick-target X-ray bremsstrahlung spectra in collisions of 6.5 keV and 7.5 keV electrons with thick Hf target are measured. The X-ray photons are counted by a Si(Li) detector placed at 90° to the electron beam direction. The bremsstrahlung spectra are corrected for various ‘solid-state effects’ namely, electron energy-loss, electron back-scattering, and photon-attenuation in the target, in addition to the correction for detector’s efficiency. The DDCS values after correction, are compared with the predictions of a most accurate thin-target bremsstrahlung theory [H K Tseng and R H Pratt,Phys. Rev.A3, 100 (1971); Kisselet al, Atomic Data Nucl. Data Tables28, 381 (1983)]. Also, a dependence of the absolute DDCS on atomic numberZ of the targets (₄₇Ag,₇₉Au and₇₂Hf) at 7.0 keV and 7.5 keV electron energies has been studied. The agreement between experiment and theory is found to be satisfactory within 27% systematic error of measurements. However, an apparent systematic difference between experiment and theory in the region of low-energy photons has been explained qualitatively by considering the fact that the hexagonal atomic structure of Hf offers possibly a greater magnitude of ‘solid-state effects’ in respect of blocking the low-energy bremsstrahlung photons from coming out of the target surface than does the cubic-face centered structure of Ag and Au target in similar conditions of the experiment.