His only political experience until now has been playing the role of president in the Servant of the People TV show.
The deputy head of the presidency, Serhiy Trofimov, was a producer in Mr Zelensky's Kvartal 95 studio.
A scriptwriter, studio co-founder, and producer were also awarded roles in the administration or as aides.
He has also given the job of deputy head of Ukraine's SBU security service to an old friend, Ivan Bakanov, who ran the TV studio and set up his political party.
Not all positions have gone to former entertainment professionals.
Andriy Bohdan, a lawyer who previously worked for one of Ukraine's richest men, Ihor Kolomoisky, and who had a role in Mr Zelensky's election campaign was handed the key job of head of administration.
But a row has broken out over his appointment.
Once an official under ousted President Viktor Yanukovych, he is technically barred from holding any government post under a law adopted in 2014. Mr Zelensky's team argues the president's administration is not covered by the ban - but critics firmly disagree.
Mr Bohdan said his appointment does not violate "morals or the law".
'We didn't start this war'
In one of his first interviews after the appointment, Mr Bohdan said the administration was considering putting any potential peace deal with Russia to a public referendum as well as a vote in parliament.
Ukraine has been in conflict with Russian-backed separatists for the past five years, since Russia annexed Crimea from Ukraine and the rebels seized control of parts of the east.
When he was sworn in on Monday, President Zelensky, 41, said his first task was securing a ceasefire in the east. "We didn't start this war but it is up to us to end it," he said.
In a phone-call late on Tuesday, President Emmanuel Macron of France and Germany's Angela Merkel urged Russia's Vladimir Putin to make "the necessary gestures to create conditions favourable to dialogue," the Elysée palace said.
An experienced politician, deputy foreign minister Olena Zerkal, was also appointed to the new presidential team but reportedly turned down the role. An official presidential decree on Wednesday annulled her appointment.
Among the other political appointees were:
- Serhiy Shefirm, who was a co-founder of the Kvartal 95 production company, as first aide to the president
- Yuriy Kostiuk, a scriptwriter for Kvartal 95, as a deputy of the administration
- Kyrylo Tymoshenko, founder of communications firm Goodmedia, which produces political adverts among other work
- Andriy Yermak, a lawyer and producer
Ruslan Ryaboshapka, a former member of the National Agency for the Prevention of Corruption, was appointed to another deputy role. Ruslan Stefanchuk, a lawyer, was made the president's adviser and his envoy to parliament,
Other roles went to members of Mr Zelensky's campaign team. Mr Zelensky also replaced the commander-in-chief of the armed forces.
During his inauguration speech, Mr Zelensky announced early elections - surprising many and raising questions over his authority to do so.
That move was formalised by decree on Tuesday, setting the election date for 21 July.