The substitution of three water molecules around trivalent chromium in CrBr3��6H2O with the tridentate 2,2���:6���,2������-terpyridine (tpy), N,N���-dimethyl-N,N���-di(pyridine-2-yl)pyridine-2,6-diamine (ddpd) or 2,6-di (quinolin-8-yl)pyridine (dqp) ligands gives the heteroleptic mer-[Cr(L)Br3] complexes. Stepwise treatments with Ag(CF3SO3) and KCN under microwave irradiations provide mer-[Cr(L)(CN)3] in moderate yields. According to their X-ray crystal structures, the associated six-coordinate meridional [CrN3C3] chromophores increasingly deviate from a pseudo-octahedral arrangement according to L = ddpd ��� dpq ��� tpy; a trend in line with the replacement of six-membered with five-membered chelate rings around CrIII. Room-temperature ligand-centered UV-excitation at 18 170 cm���1 (��exc = 350 nm), followed by energy transfer and intersystem crossing eventually yield microsecond metal-centered Cr(2E ��� 4A2) phosphorescence in the red to near infrared domain 13 150���12 650 cm���1 (760 ��� ��em ��� 790 nm). Decreasing the temperature to liquid nitrogen (77 K) extends the emission lifetimes to reach the millisecond regime with a record of 4.02 ms for mer-[Cr(dqp)(CN)3] in frozen acetonitrile.