The seat in Melbourne's east used to be one of the safest Liberal strongholds in the country but held it on a margin of just 2.8 per cent at the last federal election.
The contest between Labor's candidate Mary Doyle and Liberal Roshena Campbell attracted visits from both the Prime Minister and Opposition Leader Peter Dutton in recent days but history is firmly in Ms Campbell's favour.
No government has won a by-election in more than a century.
"The odds are very much against us, history tells us when something hasn't been done in 100 years the odd are very clear," Mr Albanese told supporters at Ms Doyle's campaign launch on Saturday morning.
The former unionist and finance worker is a breast cancer survivor who lives in the electorate with her family.
She used the launch to detail her connection to the local community, emphasising cheaper childcare and strengthening Medicare.
Mr Albanese characterised Ms Doyle as someone keen to reform policy rather than obstruct it, referencing the Opposition's push against recently-unveiled plans to boost the tax rate on superannuation accounts of more than $3 million.
"The Coalition just say no to everything and just having one more voice in the house that just says no will not assist the people of Aston," he added.
Ms Campbell, a barrister and Melbourne City councillor, lives in the inner north suburb of Brunswick more than 40 kilometres from Aston.
She says her family will move to the electorate if she wins and is connected to the area through her representation of local businesses.
On Saturday, Senators Jane Hume and James Paterson joined Ms Campbell out on the campaign trail as she talked up local infrastructure and measures to bring down the cost of living.
She previously unsuccessfully sought pre-selection for Casey in the outer east and if elected would become the first Liberal female MP of Indian descent in parliament.
The Aston by-election was triggered by the resignation of former minister Alan Tudge, who says he is leaving politics for health and family reasons.
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