Rafael Dudamel's men have reached the knockout round for just the fourth time in their history after coming through the group stages undefeated with five points from a possible nine.
However, having lost 17 of their 21 competitive encounters with this opposition, they are 11/2 (6.50) outsiders with bet365 to progress to the semi-finals with a shock win in Salvador.
Two of the last three meetings between this pair have resulted in draws, and you can get odds of 13/5 (3.60) on this one heading into extra-time following a deadlocked 90 minutes.
Luis Del Pino failed to regain his place in the side following the one-game suspension he picked up for getting sent off in the opener against Peru, with Ronald Hernandez likely to continue at left-back.
Giovani Lo Celso's place in the starting line-up is rumoured to be under threat after an underwhelming group stage, while German Pezzella could return at centre-back after being dropped for Juan Foyth in the Qatar game.
Considering their record in past encounters, Lionel Scaloni's 14-time Copa America champions would normally be runaway favourites against one of the only two South American nations that has never even reached a final.
However, it is hard to have much confidence considering their unconvincing group stage performances and recent record of just 10 wins in 20 fixtures.
What's more, La Vinotinto ran out 3-1 friendly winners in March's most recent encounter, meaning they have now gone three games without defeat against their more celebrated opponents.
Having held tournament favourites Brazil to a goalless draw in the group stages, a Venezuela side that has lost just once in 11 full internationals is surely worth backing at 7/5 (2.40) to at least take this game into extra-time.
Odds correct at the time of writing. Please gamble responsibly.