O'Donohoe partners Ian McKinley in a back-line which includes youth - in the shape of David Kearney, Michael Keating Brendan Macken and Niall Morris - and experience in Shaun Berne who starts at inside centre.
John Fogarty starts at hooker in a pack which includes brothers Ciaran and Rhys Ruddock, as well as Ireland international Trevor Hogan and Stephen Keogh who starts at number 8.
South African recruit Richardt Strauss is also poised for his first outing in a Leinster jersey, having been named amongst a strong replacements bench.
Looking forward to making a mark on the British & Irish Cup, Leinster captain O'Donohoe said: "Obviously it's a very important competition for Leinster - probably more so for lads who haven't been getting as much game-time as the first XV.
"It's very important for guys like myself and the Academy players, so it's important on a good few levels.
"Everyone's looking forward to the first game. Eoin (O'Malley) is back this week, he's been out for a long time. It's great to have him back.
"Then there's experienced guys like Shaun Berne who obviously are great to have there. They have a wealth of experience and that's great to feed off for the younger lads like myself."
He added: "This is the place we get seen, this is the shop window for a lot of guys to get picked for the Magners League.
"Every game's a big opportunity for us. Everyone's pretty well focused and looking forward to taking on Plymouth.
"From what I've seen of them, Plymouth play a simple but very effective game. We've looked at videos of them, they are a physical team and it should be a good challenge for us."
LEINSTER (v Plymouth Albion): Niall Morris; Michael Keating, Brendan Macken, Shaun Berne, David Kearney; Ian McKinley, Paul O'Donohoe (capt); Ronan McCormack, John Fogarty, Jack McGrath, Trevor Hogan, Ciaran Ruddock, Rhys Ruddock, Dominic Ryan, Stephen Keogh.
Replacements: Richardt Strauss, Stewart Maguire, Mark Flanagan, Paul Ryan, Simon Keogh, Eoin O'Malley, Andrew Conway.