The deal will see senior Albanian law enforcement officials based in the UK to help identify those with no legitimate claim for asylum more quickly.
The agreement between London and Tirana has been reached following an alarming rise in the number of Albanians arriving by small boat.
GB News has been told that around 6,000 Albanians have crossed the Channel so far this year.
A leaked official assessment of those arriving over a six week period in June and July revealed that 4 in 10 were Albanians.
The Home Office said Albanians reaching the UK by small boat have travelled through multiple safe countries before making the crossing and then "many make spurious asylum claims when they arrive".
A Home Office poster as part of the Albanian migrant deterrent campaign, which translates to 'You could face up to 4 years in jail and deportation for coming to the UK illegally'
Home Office
Under the new agreement, Albanians coming through this route will have "claims processed immediately," with those who have no right to be in the UK removed in a fast-tracked removal programme.
The new deal builds on a landmark "readmission agreement" signed with Albania last year.
Since then, a thousand Albanian criminals have been deported to their home country.
The Home Secretary has signed five other readmission agreements in the past 15 months, including one last week with Pakistan.
But the new Albanian agreement is unique and officials believe it will enable a much more rapid return of those deemed to be ineligible for asylum.
Priti Patel said: "Large numbers of Albanians are being sold lies by people smugglers and vicious organised crime gangs, leading them to take treacherous journeys in flimsy boats to the UK.
"This abuse of our immigration system and people risking their lives cannot go on.
"Thanks to our excellent levels of co-operation with Albania, we will take every opportunity to speed up removals of Albanians with no right to be in the UK."
Another part of the agreement between the two governments will see tailored social media adverts in Albanian, countering the false narrative being put out by the people smugglers as they tout for business.
The Albanian Minister for the Interior Bledi Cuci said he had also "discussed mid-term solutions to provide better opportunities for young people, and means of legal migration that enables skilled professionals and labour access to the UK".
The Home Office has not expanded on what that might entail, or how much it might cost.
The new deal is due to come into force from next week.
Government officials have not said how long the expedited process is expected to take in removing those arriving by small boat, only that the agreement will result in "rapid removal".
Home Secretary Priti Patel
James Manning