A new β-decaying state in 214Bi has been identified at the ISOLDE Decay Station at the CERN-ISOLDE facility. A preferred Iπ = (8−) assignment was suggested for this state based on the β-decay feeding pattern to levels in 214Po and shell-model calculations. The half-life of the Iπ = (8−) state was deduced to be T1/2 = 9.39(10) min. The deexcitation of the levels populated in 214Po by the β decay of this state was investigated via γ -γ coincidences and a number of new levels and transitions was identified. Shell-model calculations for excited states in 214Bi and 214Po were performed using two different effective interactions: the H208 and the modified Kuo-Herling particle interaction. Both calculations agree on the interpretation of the new β-decaying state as an Iπ = 8− isomer and allow for tentative assignment of shell-model states to several high-spin states in 214Po.