It's the veteran Spaniard's fourth victory in the Ardennes Classic, having taken his first win in 2006 before seemingly becoming unbeatable in Flèche since 2014.
Once again in true Flèche style, the race came down to the battle up the Mur de Huy after near 200km of racing. Valverde moved to the front of the pack early on the steep slopes of the Mur, and stayed calm as Joaquim Rodriguez (Katusha) made an early attempt to get off the front.
Dan Martin (Etixx-Quick Step) looked to be sacrificing his chances in service of teammate and last year's runner-up Julian Alaphilippe, leading out the now severely reduced pack towards the final ramps of the climb with Valverde on his wheel.
There was nothing either of the Etixx riders could do though as the finish line approached, with the pre-race favourite Valverde launching his sprint and holding off Alaphilippe all the way to victory.
It means it's the same riders on the top two steps of the podium as it was in 2015, with Martin managing to hold on to third place, with Team Sky (who lost leader Sergio Henao shortly before the race) managing to take fourth spot through Wout Poels.
Though the race did inevitably end with a bunch gallop up the Mur de Huy, attacks were frequent, particularly in the closing 30km of the race.
10 riders got up the road and gained almost three minutes in the initial break, but only four riders - Steve Cummings (Dimension Data), Matteo Bono (Lampre-Merida), Silvan Dillier (BMC), Tosh Van der Sande (Lotto-Soudal) - were able to hold out any time on the second of three ascents of the Mur de Huy with around 30km to go.
Cummings then went solo after the Mur, putting a 50 second gap into the chasers behind. But Movistar worked hard on the front, cutting the gap until they pulled the Briton back into the bunch with 17.6km to go.
Bob Jungels (Etixx-Quick Step) then reached out for long-range attempt, and was quickly joined by Valverde's teammate Ion Izagirre.
They managed to hold off the chasers for some time, with Tim Wellens (Lotto-Soudal) managing to join them with just under 10km remaining, but eventually they were brought back and the favourites prepared for a show down on the Mur de Huy, where Valverde once again proved victorious.
The riders now look towards the third and final Ardennes Classic of the year this Sunday, Liège-Bastogne-Liège. Valverde took the Monument victory last year after his Flèche success, and will be eyeing a fourth victory in La Doyenne this year.
La Flèche Wallonne 2016 (196km)
1. Alejandro Valverde (Esp) Movistar, in 4-43-57
2. Julian Alaphilippe (Fra) Etixx-Quick Step
3. Daniel Martin (Ire) Etixx-Quick Step, all same time
4. Wout Poels (Ned) Team Sky, at 4 secs
5. Enrico Gasparotto (Ita) Wanty-Groupe Gobert , at 5 secs
6. Samuel Sanchez (Esp) BMC Racing
7. Michael Alabasini (Sui) Orica-GreenEdge
8. Diego Ulissi (Ita) Lampre-Merida
9. Warren Barguil (Fra) Giant-Alpecin
10. Rui Costa (Por) Lampre-Merida, all same time
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