Visible luminescence between 2.0–3.5 eV of undoped and boron‐doped diamond formed by plasma‐assisted chemical vapor deposition has been investigated by cathodoluminescence. Electroluminescence from Schottky diode of boron‐doped semiconducting diamond has been observed for the first time and found to be due to the same luminescent center as that of cathodoluminescence. In the particles or films where the content of nitrogen and boron was greatly reduced, the cathodoluminescence peaks occurred at 2.8–2.9 eV. The characteristics of these emission spectra are very similar to those obtained in type‐IIa diamond where dislocations are luminescent. The doping of boron during the deposition form another luminescent center at 2.3–2.4 eV. From the monochromatic cathodoluminescence imaging, the luminescent regions differ in the two peaks. {100} sectors are much more luminescent than {111} sectors at the signal of 2.8 eV. This phenomenon has been discussed based on the difference in defect or impurity concentration of each sector.