The Potters were handed a home tie against the League Two side when the draw took place on Wednesday evening following the conclusion of the Coventry City versus Cardiff City First Round clash.
Mark Hughes will be eager to navigate a safe passage through to the Third Round as he looks to lead the Potters to their first appearance in the final of the competition since famously lifting the trophy in 1972.
The Welshman saw his side exit the Capital One Cup at the Quarter-Final stage last term, with Manchester United breaking City's hearts with a 2-0 triumph in the Potteries.
The forthcoming encounter against Pompey will be the first meeting between the two sides since 2010, when Salif Diao netted a dramatic stoppage time Premier League winner at Fratton Park.
Earlier that season the Potters were thumped 4-0 in the League Cup, and will be seeking revenge at the Britannia Stadium later this month.
The clash is scheduled to take place during the week commencing Monday 25th August. Further details will be announced in due course.
DRAW IN FULL
Burton Albion vs QPR
Port Vale vs Cardiff City
Middlesbrough vs Preston North End
Stoke City vs Portsmouth
Huddersfield Town vs Nottingham Forest
Swansea City vs Rotherham United
Watford vs Doncaster Rovers
Millwall vs Southampton
Bournemouth vs Northampton Town
Brentford vs Fulham
West Bromwich Albion vs Oxford United
Scunthorpe United vs Reading
Derby County vs Charlton Athletic
West Ham United vs Sheffield United
Swindon Town vs Brighton & Hove Albion
Leicester City vs Shrewsbury Town
Crewe Alexandra vs Bolton Wanderers
Birmingham City vs Sunderland
Gillingham vs Newcastle United
Norwich City vs Crawley Town
Bradford City vs Leeds United
Aston Villa vs Leyton Orient
Burnley vs Sheffield Wednesday
Walsall vs Crystal Palace
MK Dons vs Manchester United