Local media reports on Tuesday said that at least 46 people were believed to have been killed in the attack, up from an initial death toll of 22.
The victims were part of a group of people abducted in Maguindanao province by around 100 armed men.
Among those killed were the wife and family members of Esmael Mangudadatu, a local politician, as well as journalists.
The army has linked the killings to political rivalries ahead of next year's local elections.
In a televised address to the nation on Tuesday afternoon, Arroyo said she was determined that those behind the killings would be held "accountable to the full limit of the law".
"Additional troops have also been deployed to the area last night to further secure the area," she said.
Earlier officials in the president's office said she had ordered a state of emergency in the area, following what they said was the worst political violence seen in the country in recent history.
Lieutenant-Colonel Romeo Brawner, a spokesman for the Philippines military, said that about 500 more soldiers had been sent to Maguindanao province on the island of Mindanao "to go after the criminals" believed to be behind the killings.
He said the troops were under orders to arrest the followers of Andal Ampatuan, the incumbent governor suspected of being behind the killings.
"We maintain the Ampatuans are the suspects," Brawner told the AFP news agency.
On Monday, the military said 22 bodies - most female, some beheaded and mutilated - had been found in a mass grave in a remote mountainous area.
Al Jazeera's Marga Ortigas, reporting from the Philippines, said Ampatuan is known to be closely-associated to the government and a close ally of Arroyo so people are watching to see what action the government will take.
Meanwhile Mangudadatu, whose family members, including his wife, were among those killed according to the military, told local radio that at least four people had survived the attack.
He said the survivors were safe under his care and "will come out at the right time".
Mangudadatu told local television network ABS-CBN on Monday that he had been warned about the dangers of standing for the governorship against Ampatuan.
Mangudadatu said he stayed behind in the capital Manila and sent his wife, Genalyn Tiamzon-Mangudadatu, to file his nomination in Maguindanao on his behalf.
Maguindanao is one of the most politically tense provinces in the country.
The governor position is hotly contested because it is the seat of the autonomous region of Muslim Mindanao, she said.