Kuerten and Andre Baran lost 6-3, 6-3 to Italy's Fabio Fognini and Filippo Volandri. The 31-year-old Kuerten, who held the No. 1 ranking in December 2000, announced last month he will retire from professional tennis after the French Open, which starts May 26 at Roland Garros.
He won the last of his 20 ATP Tour titles in 2004, before he had hip surgery.
Also Monday, top-seeded Carlos Moya of Spain defeated countryman Santiago Ventura 6-4, 4-6, 6-4.
Ecuador's Nicolas Lapentti beat wild-card entry Thomas Bellucci of Brazil 6-2, 6-2 and eighth-seeded Albert Montanes of Spain downed France's Nicolas Devilder 6-4, 6-4.
Italy's Fabio Fognini defeated Jiri Vanek of the Czech Republic 6-3, 6-7 (4), 7-6 (3), and Serbia's Boris Pashanski had a 6-4, 6-4 win over Argentina's Martin Vasallo Arguello.