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When Ukrainian words, such as personal or place names, are written in the Roman script, they need to be transliterated from the original Cyrillic script. This is not a straightforward process, for two main reasons: firstly, because some sounds in Ukrainian do not have equivalents or near-equivalents in the target languages (and vice versa); secondly, because various transliteration systems have been created over time, mainly by libraries and standardisation organisations, to satisfy different requirements (see, for example, the Wikipedia article on this topic).
The most recent, and arguably the most user-friendly, system for transliterating Ukrainian for the use of English speakers is the Ukrainian National Transliteration Table, drawn up in 1996 in Ukraine and employed by the UN and the foreign ministries of many countries. It uses a logical system of equivalents for letters of the Ukrainian alphabet and allows for the omission of apostrophes and softening marks. Ukrainian words appearing on this site are transliterated using this system (with some exceptions, e.g. when a different transliteration of a personal name is widely known).
In the past Ukrainian geographic and personal names have often been transliterated into western languages not directly from Ukrainian but through Russian or the languages of other nations in power in various parts of Ukraine at various periods in its history. For instance, the direct transliteration of the name of Ukraine's capital city is Kyiv, as distinct from Kiev, which is the transliteration of the corresponding Russian word. Other examples include Lviv/Lvov, Kharkiv/Kharkov, Dnipro/Dnepr, Olha/Olga, Andrii/Andrei, etc. The 1996 decision regarding the Ukrainian National Transliteration Table states that tansliteration should be made directly between Ukrainian and English without the use of intermediary languages.
Ukrainian National Transliteration Table