The triple α-decay chain 114Ba → 110Xe → 106Te → 102Sn has been directly observed for the first time, following the 58Ni(58Ni ,2n) reaction. Implantation of 114Ba nuclei into a double-sided silicon-strip detector has allowed their α decays to be correlated in position and time with the α decays of the daughter (110Xe) and granddaughter (106Te) nuclei. In total, 17 events have been assigned to the 114Ba → 110Xe → 106Te → 102Sn triple α-decay chain. The energy of the 114Ba α decay has been measured to be Eα = 3480(20) keV, which is 70 keV higher than the previously measured value, and the half-life of 114Ba has been measured with improved accuracy, to be 380+190 −110 ms. A revised Q12C value of 19 035(45) keV for 114Ba is presented.