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 yesterday
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 amid reports that other women have missed out on frontbench positions.
Fairfax Media understands 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.
Former communications minister Stephen Conroy will be deputy Senate leader, replacing Senator Collins in the role.
Newly-elected MP for Newcastle, Sharon Claydon, wrote on Twitter there were ‘‘11 great women’’ in the shadow ministry.
The Herald Sun online reported one of the biggest winners was NSW backbencher Michelle Rowland, who was nominated by the Right faction.
Former prime minister Julia Gillard offered her congratulations to Ms Plibersek.
‘‘Congratulations to Tanya Plibersek on becoming Labor’s Deputy Leader. A woman of achievement & vision, wit & warmth,’’ she tweeted.
Labor MP Kate Ellis tweeted that she was ‘‘very excited about the fabulous tanya—plibersek being elected Deputy Leader’’.‘‘Great team, motivated to stand up for our community,’’ she wrote.