The pair have a combined 175 international appearances and 38 goals between them.
Julie Dolan Medallist Emily van Egmond and Kyah Simon were named vice captains.
De Vanna, who made her international debut in 2004, has had a distinguished career as a Matildas stalwart but one that has been marred by controversy.
The lighting fast 30 year-old attacker, who will feature in her fourth World Cup campaign in Canada, admitted to being shocked and brought to tears by the honour of being named co-captain.
"I was a little bit shocked when I was told I would be a captain," De Vanna said.
"I’ve been in this team for a very long time and a lot of the girls know how passionate I am and how much I go out and play with my heart on my sleeve for this team, so when Staj told me I was going to be a co-captain I cried.
"I love what I do and I love playing for my country, and to go out there and lead my country with the talented team we’ve got, I honestly believe this team can go all the way and leave a legacy."
Matildas coach Alen Stajcic said Polkinghorne and De Vanna were fitting choices to share the role and exemplified the values of the squad.
"Over the last four or five months we’ve done an extreme amount of work in terms of leadership and growing the team off the field, and these two have exemplified that more than others," Stajcic said.
"I’m really proud of Clare (Polkinghorne) who has been in the role before, but for Lisa De Vanna, the amount that she’s grown has been unbelievable."
Defender Polkinghorne captained the Matildas at last year’s AFC Women’s Asian Cup.
"Obviously it’s a massive honour leading the girls into a World Cup," the 26 year-old said.
"I’ve been lucky enough to share the co captaincy role the last couple of years but this is extra special being on the World Cup stage.
"I think heading into this World Cup we have set high standards for ourselves as a team, and with the talented group we’ve got there is a lot of potential to go deep in the tournament."
The Matildas will play a farewell match against Vietnam on Thursday at Jubilee Oval in Kogarah (kick-off at 6.30pm AEST) before the squad departs for Canada on Saturday.
