The field effect is used as a method of investigation of the hopping conduction in monocrystalline β‐rhombohedral boron of high purity in the temperature range 130 to 330 K. The hopping of holes between so called special localized valence (SLV) states is confirmed. The share of this thermally activated hopping via SLV states in the conductivity of boron depends on the position of the Fermi or quasi‐Fermi level. The mobility of holes in the SLV states equals 5 × 10−3 cm2/Vs at room temperature and depends exponentially on reciprocal temperature with an activation energy of about 0.1 eV.