Decay spectroscopy of the long-lived states in 186Tl has been performed at the ISOLDE Decay Station at ISOLDE, CERN. The α decay from the low-spin (2−) state in 186Tl was observed for the first time and a half-life of 3.4+0.5−0.4 s was determined. Based on the α-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 186Tl(10(−)) state [T1/2=3.40(9) s], which was known to decay solely through emission of 374-keV γ-ray transition, was extended and a lower limit for the β-decay branching bβ>5.9(3)% was determined. The extracted retardation factors for the γ decay of the 10(−) state were compared to the available data in neighboring odd-odd thallium isotopes indicating the importance of the πd3/2 shell in the isomeric decay and significant structure differences between 184Tl and 186Tl.