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Before lift-off from the Texas desert, the 90-year-old said he was looking forward to seeing Earth from an entirely new perspective, expecting to be 'entranced' by the view.
Shatner, who famously played Captain James T Kirk in the Star Trek franchise, has hitched a ride with three others in the Blue Origin sub-orbital capsule, developed by Amazon founder Jeff Bezos.
The trip is due to last around 10 minutes, hopefully giving Shatner plenty of time to gawp at the 'beauty' of Earth from space as he climbs to a maximum altitude just above 100km (60 miles).
In a video posted on Twitter by Blue Origin ahead of his 'adventure', the star said: "I'm going up into space, I don't know how many people can say that.
"It's life-changing in its way - not because of the aerial adventure, but because of the people I'm meeting and talking with."
Shatner continued: "We are just at the beginning, but how miraculous that beginning is. How extraordinary it is to be part of that beginning.
"There is this mystique of being in space and that much closer to the stars and being weightless.
"I shall be entranced by the view of space. I want to look at that orb and appreciate its beauty and its tenacity."
"We are just at the beginning, but how miraculous the beginning is." @WilliamShatner is ready to go to space. #NS18 pic.twitter.com/u3MnOAbWtW
- Blue Origin (@blueorigin) October 12, 2021
He added: "There is an adventure in my life that I would not have had, had I not done this."
Shatner is travelling with Blue Origin vice president Audrey Powers, Chris Boshuizen, who co-founded Earth-imaging satellite company Planet, and Glen de Vries, an executive with French healthcare software corporation Dassault Systèmes.
The four have had a couple of days of training, but as the New Shepard rocket is fully automatic, they should mostly be able to sit back and enjoy the ride.
However, Blue Origin flight director Nicholas Patrick said they did need to know what to do in the event of an emergency and to recognise the normal bumps and noises of space travel.
The former NASA astronaut added: "The third thing the training does is teach the crew how to behave in Zero G; how to move around the cabin without bumping each other or kicking each other; what handholds to use; the kinds of things they can expect and their response to it."
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