The Bayern Munich forward was a surprise omission from the starting lineup for Thursday's 3-0 win over Greece, as Ollie Watkins started up top and opened the scoring in Athens.
However, interim boss Lee Carsley confirmed that he planned to bring Kane - who admitted that he was a bit shocked at being dropped - back into the XI for his last game in charge, and the Three Lions captain will lead the line against the Boys in Green.
Kane is one of three new faces in the hosts' XI for their closing League B Group 2 encounter, as Newcastle United's Tino Livramento will win his first cap for the Three Lions at right-back thanks to Ezri Konsa's injury.
Konsa hurt his hip in the win over Greece and has returned to Aston Villa to undergo treatment, so Kyle Walker starts alongside Marc Guehi in the centre as Livramento takes his place on the right-hand side.
The former Chelsea youngster is one of two Newcastle players making their full England debuts on Sunday, as Lewis Hall has also been brought in for his first start after coming off the bench for his senior baptism in Greece, meaning that Rico Lewis makes way.
Ireland to play five at the back against England?
However, Carsley has seen no need to alter the midfield setup of Conor Gallagher and Curtis Jones, while Jude Bellingham, Noni Madueke and Anthony Gordon also reprise their roles in attack.
Meanwhile, Ireland head coach Heimir Hallgrimsson has made three alterations to the side that beat Finland 1-0 on Thursday, and the visitors could very well be lining up with five at the back.
Mark McGuinness and Dara O'Shea have both been drafted into the first XI in place of Mikey Johnston and Matt Doherty; O'Shea will likely feature on the right-hand side in place of the dropped Doherty.
McGuinness joins Nathan Collins and Liam Scales in the heart of the backline, while Jayson Molumby is a straight swap for the banned Jason Knight in midfield as expected.
Despite suffering an injury scare in his side's win over Finland, Festy Ebosele has been cleared to start again, and Evan Ferguson holds his place up front over Troy Parrott and Tom Cannon.
England will be automatically promoted to League A with a win at Wembley, but Ireland are already guaranteed to finish third and will therefore compete in a relegation playoff next year.
England starting lineup: Pickford; Livramento, Walker, Guehi, Hall; Gallagher, Jones; Madueke, Bellingham, Gordon; Kane
Subs: Henderson, Trafford, Lewis, Gibbs-White, Gomes, Quansah, Harwood-Bellis, Watkins, Rogers, Bowen, Solanke
Ireland starting lineup: Kelleher; O'Shea, Collins, Scales, McGuinness, O'Dowda; Ebosele, Cullen, Molumby, Szmodics; Ferguson
Subs: O'Leary, Travers, Doherty, Parrott, Johnston, O'Brien, Moran, Azaz, Manning, Coventry, McAteer, Cannon