Backed by Tennis Australia,
Instead of treading carefully after again being warned about his behaviour by the Australian Olympic team boss, Kyrgios took to Twitter to respond before launching a Facebook poll on whether he should go to Rio.
Chiller set the scene for fireworks in the wake of Bernard Tomic's Rio withdrawal on Friday when she claimed Kyrgios did not understand what it meant to be an Australian Olympian.
TA poured more fuel on the fire when it later released a statement backing world No.20 Kyrgios as the country's brightest Olympic tennis medal at Rio.
However, Kyrgios upped the ante with his social media response.
He took exception to Chiller's claim that he was coming off an ITF suspension.
Kyrgios received a fine and suspended ban last August for his crude "girlfriend" sledge of Stan Wawrinka.
"Coming out of suspension? What on earth are you talking about? I was never under a suspension ??????" he tweeted.
He stirred the pot further with his Facebook poll that asked followers whether he should go to Rio.
"It's hard not to read all the stuff written about me ... So I want your opinion," he posted.
"Fiery passion and intense competitiveness to me the things that represent the elite level of sport.
"If you think the Australian Olympic tennis team would be better without me then comment on this photo ... BUT if you were the selector and you would want me out there battling for a medal LIKE and SHARE this picture."
He quickly received almost 600 likes and 58 shares.
TA made clear where their loyalties lay following Chiller's comments on Friday.
"Since the disciplinary action taken against Nick last year, he's made a concerted effort to improve his performance and behaviour, and full credit to him," TA president Steve Healy said.
"It's unfortunate that he's been included unfairly in recent discussions on player behaviour that have not involved him."
Chiller would not speculate on whether world No.22 Tomic had beaten selectors to the punch by ruling himself out of the Rio Games on Friday.
But she made it clear what she thought of Kyrgios, saying she would be appalled if anyone repeated his antics at an Olympics.
Tomic and Kyrgios were placed on notice by Chiller last week after a raft of behavioural issues on and off the court.
Kyrgios made light of it via social media, referring to the team boss as "that Kitty Chiller", and all but dared selectors to overlook him for Rio.
"I think some of Nick's comments in social media have shown that maybe he doesn't understand what it means to be an Australian Olympian," Chiller said on Friday.
