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Chelsea beat Aston Villa 3-0 for their 600th Premier League victory to move joint top of the standings alongside Manchester United.
Lukaku needed only 15 minutes to get off the mark for the Blues after his reported 97.5 million pounds transfer from Inter Milan.
The Belgium international is in line to feature against Arsenal in the Premier League on Sunday.
Roma confirmed the 40 million euro ($47.08 million) deal for the 23-year-old, who joins Jose Mourinho's team in search of game time.
A Chelsea statement did not mention the agreed transfer fee, but media reports say the deal is worth a club record 97.5 million pounds ($134.7 million).
Belgium were among the favourites for the tournament, having spent more than 1,000 days at the head of the FIFA rankings.
Italy set up a semifinal clash against Spain after first half goals from Nicolo Barella and Lorenzo Insigne led them to a 2-1 win.
Romelu Lukaku will likely be the main attacking threat when Belgium takes on Italy in Munich on Friday in the Euro 2020 quarterfinals. The Inter Milan forward has scored three goals in his team's four victories so far.
Belgium, who became the third team after Italy and the Netherlands to win all three group games, will face one of the third-placed sides in the round of 16 on Sunday.
Kevin de Bruyne orchestrated a 2-1 comeback victory in their Group B match.