The "Kiev" is the English spelling that has replaced "Kiov"/"Kiow"/"Kyow" variants at the beginning of 19th century. It's closer to Ukrainian normative spelling of the times (Кїєвъ, which transliterates to Kiev), rather than Russian (Кіѣвъ ~Kiyev). The Russian spelling changed to "Киев" (Kiev) a full century later.
The whole "Kyiv not Kiev" debacle is mostly a political invention of yet another century later. One language cannot define correct spellings for other languages, especially the ones with different script.