Tanya Plibersek has been elected deputy Opposition Leader in a Labor caucus meeting in Canberra.
Former finance minister Penny Wong has also been elected Labor's Senate leader, the position she briefly held under Kevin Rudd's reformed government.
The appointments come after Bill Shorten was announced as new Labor leader on Sunday.
Ms Plibersek was widely expected to take the deputy's role. The former health minister, from the party's Left, received the backing of Mr Shorten - who is from the Right - early in his campaign for the leadership.
The high-profile appointments of Ms Plibersek and Senator Wong come as other Labor women have missed out on ministerial positions.
The former deputy leader in the Senate, and the No. 4 minister in the Rudd government, Jacinta Collins, has been unsuccessful in securing a place.
Outgoing speaker Anna Burke has also been unsuccessful in securing the job of chief opposition whip - that post will also go to a man, NSW MP Chris Hayes.
On Monday afternoon, Mr Shorten said that there were 11 women in his shadow ministry. This compares with seven women in Prime Minister Tony Abbott's ministry and 13 in Kevin Rudd's second ministry.
"We are on track in Labor to have more women lined up in positions of influence and importance in the shadow executive of Australia than has ever been seen either in a government or indeed in an opposition, ever," Mr Shorten said.
The Right and Left factions met separately on Monday morning to decide who to put forward at the midday caucus meeting.
The Right faction was given 16 shadow ministerial positions, the Left was allotted 13 and independents 1 - which went to ACT MP Andrew Leigh.
It is understood the Left faction was in virtual ''meltdown'' on Monday trying to allocate its share of the frontbench spots, amid fierce recriminations over the Victorian branch's desertion of Anthony Albanese in favour of Mr Shorten in last week's caucus ballot.
Mr Shorten said there were ''more talented people than places to serve'', acknowledging that some within the Labor caucus would be disappointed.
He will now take the week to assign portfolio responsibilities to his new frontbench, with plans to announce individual roles on Friday. He also has the power to appoint parliamentary secretaries.
Mr Shorten announced that there were six new faces in his ministerial team, including Mr Leigh, Western Sydney MP Michelle Rowland, Left faction powerbroker Doug Cameron, Victorian MP David Feeney, Queensland senator Claire Moore and Queensland MP Shayne Neumann.
ACT senator Kate Lundy, who was a sports minister under Julia Gillard and a minister for multicultural affairs under Kevin Rudd, is missing from Labor's frontbench. Former veterans' affairs minister Warren Snowden has similarly missed out on a spot.
Bob Carr's name does not appear on the frontbench list, following widespread reports that the former foreign minister will quit his senate seat.
Mr Rudd and former treasurer Wayne Swan have not been named on the new frontbench.
Former communications minister Stephen Conroy has come back to the frontbench, taking the role of deputy leader in the Senate.
Mr Shorten said that Labor was seeking to draw a line under its past and that his new team represented the ''strength and the unity of purpose for Labor''.
He praised Ms Plibersek as a ''remarkable Australian'' who was a respected member of caucus with a distinguished record of public service.
Mr Shorten said that the new deputy leader also reflected the Australian story - as the daughter of Slovenian migrants.
Ms Plibersek said that Labor had three important tasks in the coming months: to defend its legacy, continue to explain its vision for the future and to build a united party.
She also reflected on her family's background, saying she did not think there were many countries in the world where someone whose parents came with ''nothing but a suitcase each'' could aspire to being a member of parliament.
with Mark Kenny