Spain suffered a first loss since November 2018.
On the other hand, Germany and Switzerland played out a 3-3 thriller.
Teams from League A, Group four were in action, with rest of the heavyweights to play tonight.
Here we present the key numbers from Group A4.
Spain are atop the standings with seven points from four games. This was their first defeat in the Nations League 2020-21.
Germany have collected just one win, besides settling for three draws to stay second.
Meanwhile, Ukraine collected their second win and raced to six points.
They are below Germany on goal difference.
Switzerland stay bottom with two points so far.
Spain had 21 shots in total but Ukraine needed just one to score from their two and seal the deal.
Substitute Viktor Tsygankov ran on to West Ham forward Andriy Yarmolenko's pass to beat David de Gea, who was caught out of position on the counter-attack.
Luis Enrique's side lost for the first time since Croatia beat them 3-2 in November 2018.
Spain have failed to score in two of their last three games (0-0 in a friendly vs Portugal and 1-0 against Ukraine in the Nations League.
According to Opta, they had scored in each of their previous 42 matches (121 goals, 2.9 goals per game).
Meanwhile, Ukraine beat Spain for the first time in their history.
Germany mid-fielder Toni Kroos earned his 100th cap for Germany, becoming only the 12th player to do so.
Since his debut for Germany in 2016, Bayern Munich's Serge Gnabry has scored the most goals for the side (14 in 15 matches).
He is followed by Timo Werner (13 in 33 matches) and Leon Goretzka (12 in 26 games).
⚽️ Ukraine, Luxembourg, Malta Faroe Islands register #NationsLeague victories! 🎉🎉🎉— UEFA Nations League (@EURO2020) October 13, 2020
Result of the night belongs to _____________ 🤔
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