The peloton will face 10 categorised climbs over the lumpy and long 258km of racing which should take some six hours to finish.
Valverde (Movistar) has three career wins at Liège and his versatile and dynamic racing style is well suited to the demands of the oldest monument in cycling.
But racing is never a one-man show as 2016 proved when Team Sky's Wout Poels beat Michael Albasini (Orica-Scott) and Rui Costa (Bahrain-Merida), while Valverde finished 16th.
Injury has ruled Poels out of a title defence and Valverde is on form with 10 victories in 2017 including a fifth career win at Flèche Wallonne.
So where will the challenges come from in 2017?
Dan Martin (Quick-Step Floors) is a likely suspect and has a 2013 win to back up his claim, so has Australia's Simon Gerrans (2014) who will team up with Albasini for a two-pronged Orica-Scott attack on Valverde and Martin.
Orica-Scott will have options galore at Liège, fielding a team which includes Adam and Simon Yates, Roman Kreuziger, Damien Howson, Daryl Impey and Chris Juul-Jensen.
“Our strength will be in numbers on Sunday,” team director Matt White said. “Riders that featured on the podium at Fleche Wallonne, like Valverde and Martin, are the clear favourites.
“While we don’t have one of them, we do have a number of guys that can feature in the last hour and we will be trying to use that to our advantage in order to challenge.”
Even without Poels, Team Sky will have Sergio Henao and Michal Kwiatkowski in the hunt while AG2R La Mondiale will place its hopes on Romain Bardet.
"If I end up with Valverde on the last curve to the left, I'm doomed, Bardet said. “So I need to attack much earlier. Many riders are in the same situation so they all have an interest in going for it."
Kwiatkowski, on the other hand, will rely on Sky's collective strength to lead him to victory.
“I don't think keeping Valverde's wheel is the best solution. But I know we have to believe in ourselves. I'm here but the team also has Henao, [Gianni] Moscon and [Diego] Rosa."
BMC, which sports the rider who is perhaps the best of the season so far, Greg van Avermaet, will instead look to 2008 Olympic champion Sammy Sanchez for a result.
"I had good feelings at Flèche Wallonne," Sanchez said. "I raced cautiously and in the finale, my legs were not too bad. For me, it was the perfect test to arrive in top condition for Liège-Bastogne-Liège.
"I think we have a super strong team with Dylan Teuns, Greg Van Avermaet and myself, as we have a lot of possibilities. The course has changed and it is slightly easier than last year. There are a lot of strong competitors but I think we are capable of getting a good result."
The last word goes to Valverde, who sees the biggest challenge coming from Sky and Kwiatkowski and hopes the combined resources of two powerful teams will give him the result he wants.
"There is a hot favourite, Kwiatkowski," Valverde said. "Let's see if with two teams we can control the race. It will a be a hard day but the team feels good, I feel good and we're going for it."
Liège-Bastogne-Liège will also feature a women’s race for the first time. It's a 135.5km route with the last 45km covering the same roads as the men.
After dominating the 2016 season, Anna Van der Breggen (Boels-Dolmans) has already won the Amstel Gold Race and the Flèche Wallonne in the past week.
To achieve a hat-trick in the race which actually runs from Bastogne to Liège, she will have to control rivals such as team-mate Liz Deignan and Katarzyna Niewiadoma (WM3 Energie), who followed her to the podium at both Amstel and Flèche.
“If you had asked me last year which race I wanted to be added to the women’s calendar, I would have said Liège,” Van der Breggen said. “And now we have it.
“I think I’m going to love the race, it has long climbs," Van der Breggen said. “ It’s a tough race, maybe the toughest in the WorldTour, and I’m looking forward to it.”
There will be no live coverage of the women’s race but the broadcast will include a summary, before the podium presentation.