Nuclear properties across the chart of nuclides are key to improving and validating our understanding of the strong interaction in nuclear physics. We present high-precision mass measurements of neutron-rich Fe isotopes performed at the TITAN facility. The multiple-reflection time-of-flight mass spectrometer (MR-ToF-MS), achieving a resolving power greater than 600000 for the first time, enabled the measurement of 63–70Fe, including first-time high-precision direct measurements (δm/m≈10−7) of 68–70Fe, as well as the discovery of a long-lived isomeric state in 69Fe. These measurements are accompanied by both mean-field and ab initio calculations using the most recent realizations which enable theoretical assignment of the spin-parities of the 69Fe ground and isomeric states. Together with mean-field calculations of quadrupole deformation parameters for the Fe isotope chain, these results benchmark a maximum of deformation in the N=40 island of inversion in Fe and shed light on trends in level densities indicated in the newly refined mass surface.