They were a mid-table Championship club at the time, paired up against Gerard Houllier’s ambitious Reds.
But after matching them across the pitch, another Cup upset was soon complete when Nathan Blake slotted home a late goal for Rovers to send them into the last eight and create one of the Welshman’s career highs.
Liverpool v Blackburn Rovers
The FA Cup
Sixth Round Proper
4pm, Sunday 8 March 2015
Winners receive £360,000
Live on BT Sport
"Winning at Anfield any time is a special moment, but winning at Anfield and scoring the winner in The FA Cup is something you can still talk about 15 years later," Blake told TheFA.com.
"It was a special moment for me, The FA Cup was my favourite cup competition, I loved it.
"We were major underdogs as a Championship club at the time and we didn’t have a manager so Tony Parkes was standing in as caretaker."
Rovers were certainly no strangers to Anfield, the club had won the league title there less than five years earlier, but following relegation in 1999 they found themselves up against a Liverpool side who went on to win a treble of cups the following year.
And Blake believes their no-fear approach to the game proved the difference as the tie drifted towards a 0-0 draw and a replay back at Ewood Park.
"On the day, you just never know, so fight fire with fire and come out firing and you might surprise yourself," he added.
"It was quite an even match, we had a couple of youngsters in there such as Damien Duff, Damien Johnson and David Dunn and they had some great players too, Steven Gerrard was still a youngster back then.
"It was a difficult game, a real end-to-end FA Cup tie, and they paid us the respect that we were due and we managed to pip them at the end.
"Duffy played in Per Frandsen from the touchline, he took a touch and knocked it across and I didn’t even look. It was just a first-time finish, mate."
As Sunday's game draws closer, the comparisons to that Fifth Round tie will undoubtedly be made with both clubs finding themselves in similar predicaments to that campaign.
But after an impressive victory to knock out Stoke City in the last round and a 3-1 win over Swansea City in the Fourth Round, the former Cardiff City, Sheffield United and Wolves man believes Gary Bowyer’s side can follow the lead of 2000.
Watch Nathan Blake's FA Cup winner for Blackburn at Anfield in 2000
"As well as Liverpool are playing now, Blackburn are going there with complete confidence and no pressure," he explained.
"After Sunday’s result [Liverpool’s win against Manchester City], no-one is expecting Blackburn to get anything so there may be a little bit of complacency from Liverpool and some tiredness creeping in.
"I wouldn’t have thought they’ll be at high-end intensity so Blackburn have every chance of going there and nicking something.
"They have a few threats and if they can get the ball to Rudy Gestede, he’s a handful for any defence."
Blake, currently working as a non-executive director with League Two outfit Newport County and enjoying media work in Wales, admits The FA Cup is a competition to which he owes a lot.
After starting his career with hometown club Cardiff City, it was as a youngster in the 1993-94 season that The Cup gave him a platform to perform against some higher-ranked opposition.
And when a 21-year-old Blake scored a stunning winner against Manchester City at Ninian Park in the Fourth Round, it brought him into the national spotlight before he was snapped up by Sheffield United later that year.
"People talk about the magic of The Cup and it literally is like that, it’s a magical thing and the best competition in the world for me," he said.
Highlights of Rovers' FA Cup Fifth Round win at Ewood Park
"The excitement and the fact that smaller teams take on the bigger boys, and in a one-off game, anything can happen.
"I remember we played Middlesbrough in the round before [in 1994], who expected to give us a good thrashing and we drew with them at home.
"So we took them back up to their place, where they really thought they would thrash us, and I scored the winner there.
"We then had Manchester City at Ninian Park, which was massive at the time.
"They had players like David Rocastle, Terry Phelan, Tony Coton and Keith Curle playing, but they may have under-estimated us slightly as we were a really good footballing team.
"We just went for them, I scored a bit of a worldie and then Mark Grew our goalkeeper pulled off a penalty save from Keith Curle.
"That’s the beauty of it, it’s just a great competition."