Valverde was an Athletic player and also spent two spells at San Mames as coach, between 2003 and 2005 and later from 2013 to 2017.
Barca's trip to the Basque Country comes with the Catalan club on top of La Liga, with eight wins and a draw from their nine previous fixtures.
Here, Goal looks at everything you need to know ahead of Saturday's match...
Ousmane Dembele is still sidelined with a thigh injury and is unlikely to feature again in 2017. Rafinha is also out for Barcelona, with Arda Turan and Aleix Vidal both doubtful for the game against Athletic.
Jordi Alba is available again after recovering from a minor injury.
Gerard Pique was sent off for two bookable offences in the Champions League earlier this month, but Barcelona do not have any players suspended in La Liga.
BARCELONA POTENTIAL STARTING LINE-UP
Jordi Alba is set to return at left-back for Barcelona at San Mames with Valverde ready to field a strong side for the trip to the Basque Country.
Valverde could opt for 4-4-2 in Bilbao, with Luis Suarez and Lionel Messi in attack.
Gerard Deulofeu's recent return to form means he is line to feature on the right wing, although Sergi Roberto is also in contention for a starting spot in midfield.
ATHLETIC TEAM NEWS
Athletic Club have had a mixed bag of results so far in La Liga this season and lie in 11th place with 11 points after nine rounds of matches.
The Basques have beaten Girona and Sevilla at San Mames, as well as Eibar away, but have lost to Leganes, Valencia, Las Palmas and Atletico Madrid. On Wednesday, they were held to a 1-1 draw against tiny Formentera in the Copa del Rey and have won only one of their last six in the Primera Division.
Iker Muniain is sidelined with a long-term injury and will play no part against Barca, while Mikel Balenziaga and Oscar De Marcos are both doubtful.
BEST OPTA MATCH FACTS
Athletic have lost their last nine La Liga games against Barcelona, the last four without scoring a single goal.
At home, the Basque side have lost their last three La Liga games against Barcelona. They have never lost four in a row.
Ernesto Valverde has only won two of his six La Liga games as a manager against Athletic, both with Espanyol. The other four were all defeats.
Lionel Messi has scored 11 goals in his last 13 La Liga games against Athletic, but only one of those came in his three games at the new San Mames.
Luis Suarez has scored six goals in his last six games against Athletic in all competitions.
TV COVERAGE & KICK-OFF TIME
Athletic Club versus Barcelona kicks off at 20:45 local time at San Mames on Saturday and will be broadcast live from 19:40 UK time on Sky Sports Football .