"Safety of the public is not negotiable. Don't be sorry about what happened," Phiyega was quoted as saying by the Sowetan newspaper on Monday.
She was speaking at Warrant Officer Sello Ronnie Lepaku's funeral on Sunday, who was allegedly killed by protesting Lonmin miners last Monday.
On Thursday, 34 striking workers were shot dead in a clash with police near the North West mine in an attempt to disperse them from a hilltop where they had gathered.
Phiyega urged police officers to be cautious and vigilant and to wear bulletproof vests, shields and helmets at all times.
"We confront, every day, heartless criminals who are gunning for our lives," she said.
"You can put yourselves in danger a thousand times and come out unscathed or just once and not make it. You never know in advance how things will turn out and that is our line of work."
'Leave the weapons'
Lonmin Platinum called on striking workers on Monday to "leave the weapons" and return to their workplace to discuss their demands.
"We still are very optimistic that workers will show up," said Barnard Mokwena, executive vice president of human capital and external affairs.
"Only then can we sit down and review the situation and determine the next action," he said.
The illegal strike halted production at the world's third biggest platinum mine in Rustenburg.
Mokwena said the mine had never refused to talk to workers.
"We have asked workers through their structures to come through to engage management."
'Come down the mountain'
The mine's management would not go to the hilltop at Marikana to speak to miners.
"The mountain is not even on mine property … come down the mountain, leave the weapons and just come to the workplace," said Mokwena.
He said the mine had still not received any formal memorandum of demands from striking workers.
"We actually don't have anything by way of a set of demands."
Lonmin has issued an ultimatum to the illegally striking workers to return to work on Monday or face possible dismissal.
The ultimatum applied only to illegally striking rock drill operators and assistant rock drill operators who began an unprotected action on August 10, the company said in a statement on Sunday.
Lonmin CFO Simon Scott said, "The safety and security of our employees is paramount and nobody will be asked to report for duty if the police consider them in danger of reprisals."
Traditional leaders visit families
Traditional leaders on Monday headed to Marikana to offer support to workers and families.
The Daily Dispatch reported that the Eastern Cape house of traditional leaders, their North West counterparts and a delegation from the Congress of Traditional Leaders of South Africa (Contralesa) would visit the community on Monday.
Contralesa president Chief Phathekile Holomisa told the paper the delegation planned to meet with mine management and miners in their attempt to restore peace.
"We need to bring calm and peace to the area. We can't have a situation where people just kill each other over salary grievances," Holomisa said.
AmaMpondo king, Ndamase Ndamase, flew from East London on Sunday to meet the AmaMpondo workers in the mines.
The protests were believed to be linked to rivalry between the National Union of Mineworkers (NUM) and the Association of Mineworkers and Construction Union (Amcu) over recognition agreements at the mine. Workers also wanted higher pay.
Elsewhere, around 100 women arrived at the Ga-Rankuwa Magistrate's Court outside Pretoria where more than 250 protesters were expected to appear for public violence at Marikana.
One woman, Nombulelo Jali (37) wept hysterically. She said police did not know what happened to her husband Themba Khalo Jali (40), who she says was arrested on Thursday.
"I have come all the way from Harding in KwaZulu-Natal but we can't find him. We have frantically searched everywhere and we can't locate him. Police took him," said Jali.
Police officers approached the group of women and asked them to vacate the court premises. – Sapa-AFP