Nitrogen doped gallium selenide single crystals are studied through Hall effect and photoluminescence measurements in the temperature ranges from 150 to 700 K and from 30 to 45 K, respectively. The doping effect of nitrogen is established and room temperature resistivities as low as 20 Ω cm are measured. The temperature dependence of the hole concentration can be explained through a single acceptor‐single donor model, the acceptor ionization energy being 210 meV, with a very low compensation rate. The high quality of nitrogen doped GaSe single crystals is confirmed by photoluminescence spectra exhibiting only exciton related peaks. Two phonon scattering mechanisms must be considered in order to give quantitative account of the temperature dependence of the hole mobility: scattering by 16.7 meV A′1 homopolar optical phonons with a hole‐phonon coupling constant g2=0.115 and scattering by 31.5 meV LO polar phonon with a hole Fröhlich constant αh⊥=0.741.