Structural and electronic properties of stoichiometric single-phase CrN(001) thin films grown on MgO(001) substrates by radio-frequency N plasma-assisted molecular-beam epitaxy, are investigated. In situ room-temperature scanning tunneling microscopy clearly shows the 1×1 atomic periodicity of the crystal structure as well as long-range topographic distortions which are characteristic of a semiconductor surface. This semiconductor behavior is consistent with ex situ resistivity measurements over the range 285 K and higher, whereas below 260 K, metallic behavior is observed. The resistivity-derived band gap for the high-temperature region, 71 meV, is consistent with the tunneling spectroscopy results. The observed electronic (semiconductor/metal) transition temperature coincides with the temperature of the known coincident magnetic (para-antiferro) and structural (cubic-orthorhombic) phase transitions.