Bagpipes competed for attention with hundreds of revving engines as the convoy set off from the NSW Police Wall of Remembrance in The Domain, in inner Sydney, to the National Police Memorial in Canberra.
NSW Premier Barry O'Farrell bade the riders farewell.
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"This is a reminder for the community at large of the risks that police officers across the state and across the nation undertake every time they step outside a police station," he said.
NSW Police Commissioner Andrew Scipione said some 600 officers and supporters rode from Sydney in Saturday's event. Hundreds are expected to join them on the road to the nation's capital, taking the convoy to 1500.
"Wall to Wall is all about mates remembering mates," he told reporters before a memorial ceremony at the Wall of Remembrance.
"Old friendships will be rekindled, there will be new friends made, we'll get a chance to talk about old war stories but most importantly we'll get a chance to remember those that have fallen."
Mr Scipione said too many police were dying on the job.
Singled out for special mention was Senior Constable David Rixon, who was fatally shot during a routine traffic stop in Tamworth in March.
"In NSW we've lost 251 officers over the last 150 years. Unfortunately we've lost one this year whilst on duty and we've lost many other good friends whilst they've been off duty," Mr Scipione said.
Hundreds of men and women in leather jackets gathered under the sun for the morning memorial service where widow Louise Kenny laid a wreath in honour of Sergeant Brian Kenny.
The Kings Cross officer - BJ to his mates, who turned out in force - was killed when the motorcycle he was riding hit a truck in July.
Ms Kenny said her late husband would ride in spirit.
"Brian is still here today. Brian's spirit will continue to be remembered and he will still be in the NSW Police," she told reporters.
"The police force has been amazing. I feel as if I've got about 16,000 more family members than I had prior to losing Brian."
Ending her emotional address, Ms Kenny said she wished she had been a police officer herself.
"You are," Mr Scipione told her as she moved away from the press pack. "You're part of the family."
