Huber and Raymond entered this event 24-4 on the year with a WTA-best four titles. Meanwhile, their second round opponents - Dominika Cibulkova and Janette Husarova - had been 0-6 together dating back to 2007 before getting their first win in Monday's first round. That being said, Husarova did come into Madrid with a bit of confidence, having netted her 25th career doubles title and first in four years in Budapest last week alongside Magdalena Rybarikova.
It appeared it would be another early exit for the Slovaks, though, as Raymond served for the match at 64 54. Cibulkova and Husarova broke but soon found themselves down 6-4 in the tie-break. They reeled off four straight points to force a match tie-break. Once again, the top-seeded Americans seized the momentum in going up 7-3. They eventually had five match points in the tie-break and a total of seven in the match. But Cibulkova and Husarova would not be denied, converting on their first match point for a 46 76(6) 1513 triumph.
There was another significant second round upset, with Ekaterina Makarova and Elena Vesnina scoring a 63 62 victory over No.3 seeds Andrea Hlavackova and Lucie Hradecka, each of whom came into this week with career-high doubles rankings - No.7 for Hlavackova and No.8 for Hradecka. Makarova and Vesnina had joined forces just once before this event - a Fed Cup match in 2008 - but now find themselves in the quarterfinals against Argentines Gisela Dulko and Paola Suárez.
"We won our doubles against a very good team," Vesnina tweeted. "I'm happy with the way we both played. Tomorrow a day off, finally!"
One seeded team did make the quarters, as fourth-seeded Maria Kirilenko and Nadia Petrova beat Marina Erakovic and Monica Niculescu, 63 62, in the Russians' first match since capturing their biggest title to date in Miami.
The first round also wrapped up Tuesday, with No.5 seeds Sara Errani and Roberta Vinci, No.7 seeds Yaroslava Shvedova and Galina Voskoboeva, Julia Goerges and Samantha Stosur and Nuria Llagostera Vives and María José Martínez Sánchez all victorious.
The win was especially significant for Llagostera Vives and Martínez Sánchez, in that it was their 100th as a duo. Prior to Madrid, they had not teamed up since the 2011 Australian Open, but they have quite a résumé, highlighted by a WTA-best seven titles in 2009, one of which was the WTA Championships.
Wednesday's schedule includes a second round showdown between second-seeded Kveta Peschke and Katarina Srebotnik and Goerges and Stosur.