Brazilian Alves joined the club for a record £12.7m in January 2008 and left 19 months later - having scored just 13 goals in 50 games.
Alves claims he is still owed money for image rights.
Middlesbrough chairman Steve Gibson has dismissed the claim as frivolous and demeaning but said the club was unable to comment further for legal reasons.
Alves is the second former star to sue the club in the last fortnight after Turkish striker Tuncay claimed more than £500,000 in image rights.
The striker's representatives have lodged a High Court claim for more than £300,000 they allege is owed by the club, along with damages, interest and costs.
Willowshire Limited, which has its registered office in the British Virgin Islands, claims that the outstanding money relates to image rights for Alves.
The claimant maintains it agreed to grant to Middlesbrough certain rights on an exclusive basis.
In return, the club is said to have agreed to pay Alves 160,000 euros within 14 days of the contract being signed on September 19, 2008.
There was to be a further 600,000 euros by way of instalments, according to the claim.
The club made payments of 66,666 euros within 14 days of the agreement being signed and also on September 1, 2008, and the sum of 160,000 euros. But it is claimed Middlesbrough failed to hand over payments due on February 1, 2009, and on subsequent dates.
IPS Law LLP, representing Alves, wrote to the club demanding the money be paid by November 20 last year or court proceedings would be issued.
The club's solicitors wrote back, denying any contractual obligation to pay the outstanding sums, according to the claim.
Alves' solicitors claim their client has suffered loss and damage as a result.
They allege the total sum due is 466,668 euros and are also claiming damages, interest and costs.
In a separate action reported earlier this month, a company representing Tuncay is pursuing more than half a million pounds which it claims is outstanding to the Turkish international for sporting and economic rights and image rights.
Sundew Trading Ltd, which has its registered office in Funchal in Madeira, maintains that agreements were made between Middlesbrough and Tuncay to pay him £3,544,677 for the rights.
It says that £3m was paid by Middlesbrough to the Turkish international, but the balance of £544,677 has never been handed over.
Agent Mikel Eiguren Arano also produced a writ against Middlesbrough for £400,000 plus interest, which he claims is owed to him.
Source: Northern Echo
Source: Northern Echo