With the two final matches happening simultaneously, Slovakia and Romania drew 1-1 in Frankfurt while Ukraine and Belgium played out a goalless draw in Stuttgart.
Those results left all four teams tied on four points after three matches, something that has never happened before in the history of the European Championship.
Romania went through to the last-16 as group winners, while Belgium joined them as group runners-up. Slovakia have also qualified for the first knockout round as one of the four best third-place teams.
Because of the results in Group E, head-to-head records could not be used to determine the final positions.
Romania and Belgium both have a goal difference of +1, but Romania took top spot by virtue of scoring more goals (four vs two).
Slovakia finished third with a goal difference of zero, while Ukraine finished bottom due to their goal difference of -2.
Ukraine became the first nation ever to fail to progress to the knockout rounds with four points.
Never before at a European Championship have all four teams in a group finished on four points after three matches.
That scenario has only happened once before at a World Cup; at the 1994 tournament in the United States, Mexico, Ireland, Italy and Norway all tied on four points in Group E.
Norway were eliminated after scoring fewer goals than third-place Italy. The Italians went on to reach the final, which they lost on penalties to Brazil.