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Monaco had never beaten the Spaniard in two prior meetings and it looked like he would fall again, but used a dominating final two sets to take the win and will now try to reach his third finals at this event.
He also reached the title contest of this clay-court event in 2010 at Santiago, and 2008.
In other quarterfinal action, seventh-seeded Carlos Berlocq grounded qualifier and fellow Argentine Federico Delbonis 6-3, 6-4, and Frenchman Jeremy Chardy downed Portugal's Frederico Gil 6-2, 7-6 (7-5).
The 2012 Vina del Mar champion will collect $71,900.
The Russians can wrap up the best-of-five tie on Sunday with one more victory.
Russia, last year's Fed Cup runner-up to the Czech Republic, is a four-time Fed Cup champ and beat Spain in the final for its last title in 2008. The Russians own a 5-1 advantage against the Spaniards in Fed Cup play.
This weekend's winner will meet the Belgium-Serbia victor in the semifinals in April.
Ranked 121st in the world, Tsurenko not only drew the Ukrainians even, she completely dominated the 11th-ranked Schiavone in a 6-1, 6-2 rout. Schiavone committed 42 unforced errors and managed a mere 10 winners in the 71-minute dismantling.
Italy has won three of the last six Fed Cup titles, including back-to-back crowns in 2009-10. The Italians are also 3-0 all-time against the Ukraine in Fed Cup play.
Stuttgart, Germany (Sportsbook Betting Lines) - Petra Kvitova and Iveta Benesova each won three-set thrillers to give the Czech Republic a commanding 2-0 lead over Germany in its Fed Cup quarterfinal. Benesova gave the defending Fed Cup champions the first point with a 2-6, 6-4, 6-2 victory over Sabine Lisicki before Kvitova outlasted Julia Goerges in a 3-6, 6-3, 10-8 marathon.
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