Bryn Hughes and Paul Bone, the fathers of two murdered police officers - Nicola Hughes and Fiona Bone - had campaigned for such a recognition of those who had died in public service.
And their daughters, who were killed responding to a call in Greater Manchester in 2012, were among those honoured.
"It's been a long arduous campaign but it's been worthwhile in the end, to see so many families here today receiving it after so many years. It's been quite poignant quite, emotional at times," said Mr Hughes after the ceremony.
Mr Bone said: "It's nice to be at the end of the process and (to get) recognition finally from the state for people who have lost their lives."
Most of this initial group being honoured are from the police and fire services, but it also includes Rebecca Dykes who was killed while working for the Foreign, Commonwealth and Development Office in Lebanon in 2017.
Other groups could be eligible, such as NHS workers who died during the pandemic.
"We must never forget those who have given their lives to protect others in the line of duty," said Prime Minister Sir Keir Starmer.
"While families will never be able to replace their loved ones, the Elizabeth Emblem pays tribute to the sacrifice they have made."