The draw took place on Sunday afternoon for the third round of the FA Cup and Liverpool will face a tricky trip to north London to play the current Premier League leaders.
Liverpool's clash with Arsenal will take place on the weekend of 6 January, with the Reds likely to be broadcast on TV given the magnitude of the tie.
Jurgen Klopp's side will have faced the Gunners roughly two weeks prior to their FA Cup meeting, Arsenal travelling to Anfield in the Premier League on 23 December.
Liverpool will play Newcastle United on New Year's Day before their cup clash with Arsenal.
The Reds have played the Gunners 12 times in the FA Cup previously, winning three, drawing three and losing six of the past encounters. Despite their superior head-to-head record, Liverpool beat Arsenal 2-1 in the 2001 FA Cup final thanks to a brace from Michael Owen.
Arsenal are the side that have won the FA Cup most frequently (14 times), while Liverpool will be hunting down a ninth trophy this season.
The other standout tie is Newcastle United's trip to Sunderland in the Tyne-Wear derby.