Maamau, 64, retained his seat by a landslide in August parliamentary elections that were dominated by concerns about the cost of living, rising sea levels and relations with Beijing.
He switched diplomatic ties from Taiwan to Beijing in 2019 in the hope that the world's second-largest economy would help Kiribati meet ambitious development goals.
Maamau has been tipped as hot favourite to continue leading the nation of around 120,000 people, with his two rivals both hailing from his own ruling Tobwaan Kiribati Party.
But in a late surprise, one of those rivals -- Kaotitaake Kokoria -- recently defected from the ruling party, an election official at the interior ministry told AFP.
It is unclear if the defector will be able to muster enough votes to beat the incumbent president and the third candidate, Bautaake Beia, ruling party MP Ruth Cross Kwansing told Radio New Zealand.
Under Kiribati's electoral system, the parliament selects presidential candidates who then stand in a nationwide election.
Results from the presidential election are expected Saturday.
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