The launch is scheduled to take place at 7:00 am (1200 GMT) from the sprawling Texas base of the private space company owned by billionaire Elon Musk.
Fallback times are scheduled later in the week if Monday's attempt is postponed.
The US space agency NASA has picked the Starship capsule to ferry its astronauts to the Moon as part of the Artemis III mission, set for late 2025 at the earliest.
Starship consists of a reusable capsule that carries crew and cargo and the first-stage Super Heavy booster rocket.
The 164-foot (50-meter) tall Starship spacecraft sits atop the 230-foot tall Super Heavy rocket.
SpaceX conducted a successful test-firing of the 33 Raptor engines on the first-stage booster of Starship in February.
The Super Heavy booster was anchored to the ground during the test-firing, called a static fire, to prevent it from lifting off.
The rocket has never flown in its full configuration, powered by the first stage.
"Success maybe, excitement guaranteed!" Musk tweeted late Friday.
NASA will take astronauts up to lunar orbit itself in November 2024 using its own heavy rocket called the Space Launch System (SLS), which has been in development for more than a decade.
Starship is both bigger and more powerful than SLS.
It generates 17 million pounds of thrust, more than double that of the Saturn V rockets used to send Apollo astronauts to the Moon.
SpaceX foresees eventually putting a Starship into orbit, and then refueling it with another Starship so it can continue on a journey to Mars or beyond.
The idea of a reusable launcher, Musk's broad strategy, is to reduce the price. Each Starship flight could eventually cost "less than $10 million," he said early last year.
Other super heavy rockets under development include Blue Origin's New Glenn, China's Long March 9 and Russia's Yenisei.
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