Decay spectroscopy of the long-lived states in Tl-186 has been performed at the ISOLDE Decay Station at ISOLDE, CERN. The a decay from the low-spin (2(-)) state in Tl-186 was observed for the first time and a half-life of 3.4(-0.)(4)(+0.5) s was determined. Based on the alpha-decay energy, the relative positions of the long-lived states were fixed, with the (2(-)) state as the ground state, the 7((+)) state at 77(56) keV, and the 10((-)) state at 451(56) keV. The level scheme of the internal decay of the Tl-186(10((-))) state [T-1/2 = 3.40(9) s], which was known to decay solely through emission of 374-keV gamma-ray transition, was extended and a lower limit for the beta-decay branching b(beta) > 5.9(3)% was determined. The extracted retardation factors for the gamma decay of the 10((-) )state were compared to the available data in neighboring odd-odd thallium isotopes indicating the importance of the pi d(3/2) shell in the isomeric decay and significant structure differences between Tl-184 and Tl-186.