The 18-year-old, who has wormed his way into the Liverpool first team, earned just his second call-up to the senior England squad this month under manager Thomas Tuchel.
Having made his senior bow in a friendly win over New Zealand in June, Liverpool fans will have been excited to see Ngumoha face off against Spain in what would be one of the toughest tests of his career so far.
Five England players withdrew through injury this week, including attackers Cole Palmer and Marcus Rashford, as the pathway to the starting eleven opened up for the teenager on Saturday evening.
However, James Garner and Morgan Gibbs-White were added to the squad and as only 23 can be named in a Nations League matchday squad as per UEFA rules, Tuchel has decided to omit Ngumoha.
Ngumoha has made three league appearances for manager Andoni Iraola's Liverpool this season, but only one of them has come as a starter.
Competition is stiff amongst Tuchel's side with Bukayo Saka, Harry Kane, Dominic Calvert-Lewin, Anthony Gordon and Morgan Rogers in attack and Eberechi Eze and Morgan Gibbs-White in midfield.
As Ngumoha misses out, that leaves zero Liverpool players in the squad. Meanwhile, former Reds defender Trent Alexander-Arnold returns to the side after missing out on the World Cup over the summer.