Thiago was introduced after just 42 minutes in the Spanish capital last week as Klopp’s bold decision to start Naby Keita in the first leg backfired.
But the Spanish international, who won the Champions League with Bayern Munich last season, was again surprisingly overlooked in favour of James Milner.
Madrid boss Zinedine Zidane made just one enforced change from the first leg as midfielder Fede Valverde looks set to deputise at right-back for the injured Lucas Vazquez.
Starting line-ups for the Champions League quarterfinal, second leg between Liverpool and Real Madrid at Anfield on Wednesday (kick-off 1900 GMT, 1-3 agg):
Liverpool (4-3-3)
Alisson Becker; Trent Alexander-Arnold, Ozan Kabak, Nat Phillips, Andy Robertson; Fabinho, James Milner (capt), Georginio Wijnaldum; Mohamed Salah, Roberto Firmino, Sadio Mane
Coach: Jurgen Klopp (GER)
Real Madrid (4-3-3)
Thibaut Courtois; Fede Valverde, Eder Militao, Nacho, Ferland Mendy; Toni Kroos, Casemiro, Luka Modric; Marco Asensio, Karim Benzema (capt), Vinicius Junior