His 6-0, 6-2 thrashing of Belgium's David Goffin in the O2 Arena followed Monday's tense three-set win over Dominic Thiem when he became the first Bulgarian to take part in the elite tournament for the top eight players in its 48-year history.
The result means Ecuador have one point from two games in Group B and Venezuela have two points from three.
Colombia beat Peru 4-2 in a penalty shootout on Friday to progress to the semi-finals of the Copa America after the two sides played to a dull scoreless draw in New Jersey.
A stunning Andre Carrillo volley gave Peru their first World Cup goal in 36 years before captain Paolo Guerrero grabbed a second as the Andean nation condemned Australia to a 2-0 defeat in Sochi on Tuesday and an early exit from Russia.
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