The one-day visit is her first since the signing of the Minsk accord in early 2015, which has so far failed to achieve its aim of bringing peace to eastern Ukraine.
Talks between the chancellor and Ukrainian President Petro Poroshenko were underway at his official residence, the presidency said in a statement.
Merkel will also meet Prime Minister Volodymyr Groysman.
Talks will focus on flashpoint areas including the self-described separatist Donbass republic and Moscow-annexed Crimea, the Ukrainian presidency said.
Moscow has been accused of fuelling a rebel conflict in eastern Ukraine that has cost the lives of some 10,000 people
Analysts say the Nord Stream 2 gas pipeline, which will bypass Ukraine to bring supplies direct from Russia to Germany, will also be on the agenda.
"We know that Mrs. Merkel promised that there would be no agreement on this pipeline to the detriment of Ukraine, so Ukraine will expect new assurances," Kateryna Zarembo, analyst of the New Europe Center told AFP.
Nord Stream 2 aims to double the capacity of Nord Stream 1 by the end of 2019.
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