65Zn is a common calibration source, moreover used as a radioactive tracer in medical and biological studies. In many cases, γ-spectroscopy is a preferred method of 65Zn standardization, which relies directly on the branching ratio of Jπ(65Zn) = 5/2− → Jπ(65Cu) = 5/2− via electron capture (EC*). We measure the relative intensity of this branch to that proceeding directly to the ground state (EC0) using a novel coincidence technique, finding IEC0/IEC* = 0.9684 ± 0.0018. Re-evaluating the decay scheme of 65Zn by adopting the commonly evaluated branching ratio of Iβ+ = 1.4271(7)% we obtain IEC* = (50.08 ± 0.06)%, and IEC0 = (48.50 ± 0.06)%. The associated 1115 keV gamma intensity agrees with the previously reported NNDC value, and is now accessible with a factor of ∼2 increase in precision. Our re-evaluation removes reliance on the deduction of this gamma intensity from numerous measurements, some of which disagree and depend directly on total activity determination. The KDK experimental technique provides a new avenue for verification or updates to the decay scheme of 65Zn, and is applicable to other isotopes.