In late deals, Brazil defender Luiz returned to Chelsea after two years at Paris Saint-Germain, while France midfielder Sissoko left Newcastle United for Tottenham Hotspur.
The two moves took spending for English top-flight clubs to around £1.17 billion, according to Sky Sports – a record for a single transfer window.
“I’m delighted to return to Chelsea,” Luiz told the Chelsea website after signing a three-year contract.
“We had a fantastic story during my first time at the club and I want to help the team and (manager) Antonio Conte achieve a lot of success.”
Shaggy-haired centre-back Luiz, 29, became the world’s most expensive defender when PSG paid £50mn (B2.27bn) to prise him from Chelsea two years ago.
But he was tipped to lose his place to compatriot Marquinhos at PSG and has returned to Stamford Bridge for a reported fee of around £32mn (B1.45bn).
Chelsea also landed Spanish left-back Marcos Alonso from Fiorentina for a reported £23mn (B1.04bn), while Colombian winger Juan Cuadrado joined Juventus on a three-year loan.
Sissoko, 27, looked poised to join Everton for much of the day, only for Tottenham to reportedly gazump the Merseyside club with a late bid.
He signed a five-year contract and is thought to have cost Spurs around £30mn (B1.36bn).
“Hi fans. I’m happy to be here,” Sissoko told Spurs supporters in a video posted on the club’s Twitter page.
“I will give everything for you, for the team, and I hope we will win a lot of games and a lot of titles.”
Tottenham also signed France Under-21 winger Georges-Kevin Nkoudou from Marseille for £11mn (B500mn), with Cameroon forward Clinton Njie going the other way on a season’s loan.
Everton consoled themselves with a loan deal for West Ham United’s Ecuadorean forward Enner Valencia.
At Manchester City, five players who have fallen out of favour under new manager Pep Guardiola left on season-long loans.
England goalkeeper Joe Hart completed his move to Italian side Torino and French midfielder Samir Nasri joined Europa League champions Sevilla.
Wilfried Bony pitched up at Stoke City, French centre-back Eliaquim Mangala signed for Valencia and defender Jason Denayer joined Sunderland.
Flush from the proceeds of a new £5.14bn domestic television rights deal, Premier League clubs broke through the one billion pounds barrier in one transfer window for the first time.
Analysts believe European spending over the two-month window has easily been the highest yet.
English champions Leicester City broke their transfer record with the £29.7mn (B1.35bn) capture of Sporting Lisbon’s Algerian striker Islam Slimani, who agreed a five-year contract.
“I’ve always wanted to play in the Premier League and to get the opportunity to do that with the reigning champions was something I simply could not turn down,” Slimani said.
Sunderland were one of 13 English clubs to set a new club record during the window, signing 22-year-old Gabon midfielder Didier Ndong from French side Lorient for a confirmed fee of £16mn (B727mn).
Burnley were another, buying Irish midfielder Jeff Hendrick from Derby County for a reported £10mn.
Mario Balotelli's miserable spell at Liverpool is finally over after he joined French club Nice on a free transfer.
The wayward Italy forward scored just four goals in 28 appearances for Liverpool and spent last season on loan at AC Milan.
Arsenal’s injury-prone England international midfielder Jack Wilshere, 24, was loaned to Bournemouth after slipping down the pecking order at the Emirates Stadium.
“"Jack is a player that needs no introduction and one that, quite rightly, our supporters will be excited to see,” said Bournemouth chief executive Neill Blake.
It was a relatively quiet deadline day in Europe’s other major leagues.
In addition to Mangala, Spanish side Valencia signed Argentina international centre-back Ezequiel Garay from Zenit St Petersburg for a reported fee of 20 mn euros (B727mn).
Espanyol, who are now under Chinese ownership, swelled their ranks by signing goalkeeper Diego Lopez on loan from AC Milan and securing a loan deal for Mexico defender Diego Reyes from Porto.
In Germany, Werder Bremen signed German winger Serge Gnabry from Arsenal and Hamburg made a 10 mn euros (B386mn) move to bring Brazilian defender Douglas to the club from Atletico Mineiro.