According to prosecutors, Roxana Baldetti took a 50% cut of illegal payments channeled to officials helping businesses evade customs duties.
Roxana Baldetti was arrested last week over the scheme and denies wrongdoing.
Addressing the nation on August 23, Otto Perez Molina rejected any link to the scandal and said his conscience was clear.
Eight members of his government have resigned over the allegations and nearly 30 people detained.
In court, Roxana Baldetti – who resigned in May – spoke to confirm her identity, taking notes as prosecutors played some of the wiretapped conversations that led to her detention.
The bribery scam has become known as “La Linea”, or “The Line”, after the hotline businesses allegedly rang to clear their imports through customs at cut-price rates.
Presidential elections are being held in early September, but electoral law bars Otto Perez Molina from standing for another term.
President Otto Perez Molina has faced calls to stand down from across Guatemalan society and investigators are seeking to end his immunity from prosecution.
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