In this paper, pure thick Al (Z = 13), Ti (Z = 22), Zr (Z = 40), W (Z = 74) and Au (Z = 79) targets are bombarded by electrons in an energy range of 5–27 keV, and the experimental thick-target characteristic X-ray yields of K-shell and L-shell, the X-ray production cross sections and the ionization cross sections of inner shells are presented. The present experimental setup and data processing are improved, specifically, a deflection magnet is installed in front of the X-ray detector to prevent the backscattered electron from entering into the X-ray detector, and the bremsstrahlung background spectra calculated from PENELOPE Monte Carlo simulations are used to deduce the net peak areas. The X-ray detector used in this experiment is the XR-100SDD manufactured by Amptek Inc. with a 25 mm ²C2 ultra-thin window which can detect the low-energy x-rays down to boron Kα line (0.183 keV). Standard sources ( ⁵⁵Fe, ⁵⁷Co, ¹³⁷Cs and ²⁴¹Am) with an activity accuracy range of 1%–3% ( k= 2), supplied by the Physikalisch-Technische Bundesanstalt, Germany (PTB), are used to perform the detector’s efficiency calibration, and in a low-energy range (< 3.3 keV) the efficiency calibration is accomplished by measuring characteristic X-ray spectra produced by 20 keV electron impacting various thickness solid targets (i.e. by the characteristic peak method). The uncertainty of the detector’s efficiency calibration obtained in this paper is ~1.6%. The experimental thick-target characteristic X-ray yield data with an uncertainty of 1.7%–6.2% are compared with the PENELOPE Monte Carlo simulations, in which the inner-shell ionization cross sections are based on the distorted-wave Born approximation (DWBA) calculations, and they are in good agreement with a difference of less than or ~10%. According to the measured thick-target characteristic x-ray yields, the K-shell ionization cross sections for Al, Ti and Zr and the L-shell X-ray production cross sections for Zr, W and Au are also obtained with an uncertainty of 5%–8% (except for Al due to large K-shell fluorescence yield uncertainty), the difference between the experimental and theoretical data is also less than or ~10%. Moreover, by comparing the thick-target characteristic X-ray yields obtained from the analytical model and the PENELOPE Monte Carlo simulations at the electrons’ incident angles of 45° and 90°, it is found that the degree of agreement between the results from the analytical model and the Monte Carlo simulations at the incident angle of 90° is better than at the incident angle of 45°. Moreover, the contributions of the secondary electrons and bremsstrahlung photons to the characteristic X-ray yield are also given based on the PENELOPE Monte Carlo simulations. As for the elements studied in this paper, for the low ionization threshold energy, the contribution of the secondary electrons is ~2%, and however, for the high ionization threshold energy, the contribution is ~10%–20%. These contributions depend weakly on the energy of the incident electrons and show that these contributions are closely correlated with atomic number.