The 16 presidential hopefuls include former resistance fighter and incumbent President Francisco "Lu Olo" Guterres, independence figure and Nobel laureate Jose Ramos-Horta, and a former Catholic priest.
While the nation's so-called "guerrilla generation" of independence figures still dominate the field, for the first time there are also four female candidates, including deputy prime minister, Armanda Berta Dos Santos.
A recent poll by the national university showed that Ramos-Horta, 72, former defence force commander, Lere Anan Timur, and Guterres are the favourites, with Ramos-Horta in front with 39 per cent.
If no candidate wins an outright majority in Saturday's vote, it will proceed to a run-off on April 19 between the top two contenders.
Approaching 20 years since independence after the end of a brutal occupation by Indonesia, East Timor has for long spells struggled with political instability.
After the last elections in 2018, Guterres refused to swear in some ministers from the National Congress of the Reconstruction of East Timor (CNRT), a political party led by former prime minister and resistance leader Xanana Gusmao.
The move sparked a chain of ongoing political fractures.
In a streamed address on Thursday, Ramos-Horta, who is backed by Xanana's CNRT party, said he was running because he felt the current president had "exceeded his powers".
At an election debate, Guterres pledged to ensure peace and stability in the country and to defend its sovereignty and follow the constitution if he won a new term.