A statement released by Guatemalan Minister of Finance Dorval Carias' office announced that the minister resigned on Monday without giving a reason for his decision, but the move comes as the ministry is forming next year's budget.
After the country's attorney general asked the Supreme Court for permission to prosecute Perez over a suspected customs racket, Communications Minister Victor Corado also tendered his resignation on Monday and three other ministers stepped down over the weekend.
The president has rejected any misbehaviour and has said he will not resign.
In his address to the nation on television, President Molina rejected the accusations claiming he had received money from a customs bribery scheme, and he maintained his defense saying his conscience was clear.
However, after prosecutors last week jailed his previous vice president over the customs scandal and said they believed the 64-year-old Perez was in on the scam, the president’s post is in increasing jeopardy.
Perez as a retired general took his mission over in 2012, and cannot run to be elected again according to the laws.
His right-wing Patriot Party is way off the pace ahead of the first step of voting on September 6.
The fraud allegations urged Perez to dismiss some senior cabinet ministers in May and also puts the country's upcoming presidential elections into disarray.
The ministers of education and economy also announced their resignations, as did President Otto Perez Molina’s commissioner for competitiveness on Saturday to protest the corruption scandal that threatens the Central American country’s presidency.
The three officials who have links with Guatemala’s business chambers have called on Perez Molina to resign.
Hundreds of people who were disturbed by the unrest in the government demonstrated in front of the national palace and called for Perez for resignation, on Saturday.
Business chambers also being normally supportive of Perez Molina have asked him to resign.
Guatemalan ex-vice president appears in court to face allegations
Prosecutors in Guatemala alleged Monday that former Vice President Roxana Baldetti accepted $3.7 million in bribes as part of a customs corruption scandal that forced her from office and has shaken the government of President Otto Perez Molina.
Baldetti's appearance in court was followed by her arrest on Friday.
A crowd of dozens of people yelled "Corrupt! Thief!" during the heavily guarded hearing outside the courthouse.
"The only thing they are doing in legal terms is to state that there is a reasonable suspicion," said Judge Miguel Angel Galvez noteing the prosecutor's statements weren't formal accusations.
Prosecutors said Baldetti pocketed 50 percent of the bribes funneled to a chain of officials who helped businesses evade import duties.
However, she has denied any wrongdoing.