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If Edmund was to come through that he could face Uzbek Denis Istomin, who sensationally upset Novak Djokovic here a year ago.
Last year's quarter-finalist, Jo Konta, will be up against American Madison Brengle in the first round and could meet No 6 seed Karolina Pliskova in the fourth.
Froome will have an advantage in the time trial and brings another strong, stultifying team containing Mikel Nieve, Wout Poels and Diego Rosa.
Having come Vuelta runner-up thrice to JJ Cobo, Alberto Contador and Nairo Quintana over the past six seasons, Froome says he had “unfinished business” with the race.
In a surprise reverse Cameron Norrie was earlier knocked out of the second-round qualifying by Australian John-Patrick Smith 6-4, 6-2.
The draw did Edmund few favours, pitting him in the first round against US Open finalist Kevin Anderson, who beat him in five sets at Roland Garros last year.
Fabio Aru (Italy/Astana): The 2015 champion is back for his third Vuelta.Like nearly everyone on this list, Aru will lose at least to Froome in the time trial.Alberto Contador (Spain/Trek-Segafredo): It’s his last rodeo.The wide open women's draw threw up a fascinating section around Sharapova.The controversial Russian could meet Anastasija Sevastova in the second round, who knocked her out of the US Open last 16 in September.