Last year's champion Shahjalal and runner-up Jibon Boli did not participate in this year's competition
Valencia are yet to win in the league in seven matches under former England defender Gary Neville and face the ominous task of taking on last season's treble winners who are top of La Liga and unbeaten in 25 games in all competitions.
In their last meeting, Luis Enrique's men were held to a 1-1 draw away at Valencia in a La Liga tie last December.
Celta, surprise winners over Atletico Madrid in the last round, are up against an in-form Sevilla.
Both first-leg matches are on Feb. 3.