Five days after Valencia won a league match under him for the first time, Neville saw his players race into a five-goal lead inside 35 minutes.
Santi Mina scored twice and set up three more in a sparkling performance.
The visitors improved after the break but Rodrigo wrapped up the win.
The result matched Steaua Bucharest's competition record.
With a Champions League place at stake for the winners of the Europa League, Neville could end the season on a high despite his side being 12th in La Liga.
Earlier on Thursday, holders Sevilla beat Molde 3-0 to take control of their last-32 tie.
Former Juventus striker Fernando Llorente struck twice and Kevin Gameiro added a third as Ole Gunnar Solskjaer's men were well beaten.
Villarreal will also defend a lead next week after beating Napoli 1-0 thanks to a superb free-kick from Denis Suarez, while Borussia Dortmund took a large step towards qualification with a 2-0 home win over Porto.
Dortmund - who won the now defunct European Cup Winners' Cup in 1966 and the Champions League in 1997 - need the Europa League to complete the set of European trophies and were welcomed by an enormous banner at the Westfalenstadion.
Right-back Lukasz Piszczek put them ahead when Iker Casillas failed to keep out his original effort before forward Marco Reus buried a low shot to finish a clinical counter-attack.
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