His first season as senior was with his home town club Radnički Kragujevac during the 2007–08 season playing back then in the Serbian League West. At the end of that season he moved to the top league club Rad Belgrade entered into the senior team in the 2008–09. He played as right side midfielder.
Red Star Belgrade
Milivojević signed for Red Star Belgrade on 19 December 2011. His arrival to Red Star was largely fulfilled by the will of coach Robert Prosinečki, who insisted that Milivojević had bright potential. On 17 November 2012, Milivojević scored an impressive goal against city rivals Partizan.
On 26 July 2013, Milivojević signed a five-year contract with Belgian football giants R.S.C. Anderlecht. On 1 September 2014, it was announced that Luka Milivojević has joined Olympiacos on loan from Anderlecht. After the 2013-14 season, Olympiakos midfielder Luka Milivojević has reiterated his desire to stay at the club. The two clubs may start new negotiations after the season ends and the 24-year-old defensive midfielder has stated that his wish is to make the move permanent. According to reports in Belgium, Olympiakos will meet Anderlecht's asking price in order to complete the permanent transfer of Luka Milivojević. Olympiakos have been in negotiations with the Belgian club as they were reluctant to pay the €2,7 million Anderlecht have been asking for the 24-year-old Serbian midfielder.
On 4 June 2015, Anderlecht confirmed that it had reached an agreement with Olympiacos for the permanent transfer of Luka Milivojević. The Serbian international who has spent a season with the Mauves, joined the Greek champions by signing a four-year contract with Greek champions, on a fee of €2.3 million. On 30 June 2015, Olympiakos have turned down a bid in the region of €5 million from Fenerbahce. The Turkish club is very eager to sign the Serbian midfielder as Olympiakos ex manager Vitor Pereira is a big admirer of the player. The player stayed in Piraeus, having a vital role in back to back championship.
On 31 January 2017, Milivojević signed for Premier League club Crystal Palace for a fee believed to be in the region of £11m.  On 11 February 2017, he made his debut for Crystal Palace in the 1-0 defeat to Stoke City.  On 10 April 2017, he scored his first goal for the Eagles in a 3-0 win against Arsenal.  On 14 May 2017, he scored his 2nd goal for Palace in the 4-0 win against Hull City.  It was a game in which Palce confirmed their status in the Premier League for the following season, while condemning Hull to relegation. 
On 13 January 2018, Milivojević was made captain for Crystal Palace for the first time in the 1-0 win at home to Burnley. 2017/18 was his first full season, and in total he played 37 games (captain in 15), scoring 10 goals. 
He is member of the Serbia national under-21 football team. He had been called up for the Serbia national football team squad on 29 September 2011, to face Italy and Slovenia in the UEFA Euro 2012 qualifying phase. He made his debut for Serbia on 14 November 2012 in a friendly match with Chile.
- As of 26 August 2016
|Red Star Belgrade||2011–12||11||1||3||0||—||—||14||2|
|Serbian national team|
- Red Star
- Serbian SuperLiga Team of the Year (1): 2011–12