Watson and her partner Joe Salisbury were beaten in straight sets by number seven seeds Jan Zielinski and Hsieh Su-wei.
The match was moved to fill a gap on the Centre Court left when Alex de Minaur withdrew from his clash with Novak Djokovic.
In a clash that lasted one hour and 48 minutes, Watson and Salisbury were downed 7-6 6-4, having raced to a 4-1 lead in the opening set.
Watson lost in the opening round of the singles to her doubles partner Greet Minnen 7-5 6-4 having been given a wild card, and they went on to lose in the first round of the doubles to American’s Bethanue Mattek-Sands and Sofia Kenin 6-3 6-4.