The core-excited isomer in fully-ionized 133Sb has been directly studied for the first time by applying the novel technique of isochronous mass spectrometry at GSI. The neutron-rich nuclides in high charge states were produced by projectile fission of 411 MeV A 238U ions, separated in flight by the fragment separator (FRS) and stored in the isochronous storage ring (ESR). The measured excitation energy is 4.56(10) MeV. The neutral-atom half-life is known to be 17 μs. This is the shortest-lived isomer measured directly with mass spectrometry techniques. The extended in-flight half-life of the bare ions in the ESR, which is due to the exclusion of the strong internal conversion, demonstrates that there should be another nuclear level above that identified from isomer-decay spectroscopy, in support of shell-model calculations. This measurement opens up a new half-life domain for storage-ring measurements.