Unprecedented imido phthalocyaninato complexes of pentavalent refractory metals [PcM(NR)Cl] (M = Mo, W, Re; R = tBu: 1, 3, 6, Mes: 2, 4, 7 or Ts: 5) have been synthesized by reductive cyclotetramerization of phthalonitrile in the presence of appropriate bis(imido) complexes of Mo, W and Re as templates. While d¹Mo(V) and W(V) species 1–5 show distinctive EPR spectra corresponding to metal centered radicals with hyperfine coupling of two magnetically non-equivalent nitrogen atoms (4 equatorial and 1 axial N), corresponding d²Re(V) compounds 6 and 7 are diamagnetic. [PcMo(NtBu)Cl] 1 crystallizes from 1-chloronaphthalene in the tetragonal space groupP4/n. The molecular structure reveals, that the metal center is located above the plane of the equatorial N4 and displaced towards the axial π-donor ligand. Due to the thermodynamic trans effect the Mo–Cl bond trans to the imido group is elongated to about 2.600(2) Å.