Reigning trap world champion and rifle ace Seonaid McIntosh among first four shooters named for Team GB.
Matthew Coward-Holley is the star name in the group of Olympic debutants after becoming Britain's first ever world champion in trap in 2019.
The 26-year-old, who took up shooting seriously after suffering "almost life-changing" injuries playing rugby, made a successful switch from double trap when that discipline was dropped from the Olympic Games after Rio 2016.
While Britain is in COVID lockdown, elite athletes have been given exemption to continue training with Coward-Holley currently at a camp in the north of England.
Joining him in the squad is 24-year-old Seonaid McIntosh, the country's most successful ever female rifle shooter after winning the 50m rifle prone world title in 2018 and the 2019 World Cup Final in 50m Rifle 3 Positions which is an Olympic discipline.
The Scotswoman is the daughter of two international level shooters and her sister, Jennifer, competed at the last two Games before retiring in 2018.
Speaking to Olympic Channel from Edinburgh, McIntosh said, "I never really wanted to do shooting when I was young. I used to get dragged to events to see Jen and think it was a bit boring.
"But seeing Jen at London 2012... it was so exciting and really made me want to take it up."
Completing the list of four names announced on Wednesday are trap shooters Kirsty Hegarty, the first athlete from Northern Ireland to be selected for Tokyo 2020, and Aaron Heading.
Hegarty won silver at the 2018 Commonwealth Games and European Championships, while Heading is a four-time Commonwealth Games medallist - including gold in 2010 - and took bronze at the 2019 European Games.
On the four picked, British Shooting performance director Steven Seligmann told Olympic Channel, "They've all achieved significant major success results. They're direct quota place winners in their own right. I think each of them are going to the Games with prospects to medal."
Six shooters have also been named to the Paralympic GB squad, headed by Beijing 2008 champion and two-time London 2012 medallist Matt Skelhon.
He is joined by his partner, Rio 2016 Olympian Issy Bailey, Kirsty Barr, London 2012 bronze medallist James Bevis, Ryan Cockbill, Tim Jeffery and Lorraine Lambert.