But Serco Barclays, which operates the scheme, immediately responded saying the RMT union is not recognised by them.
It is the latest move in the escalation of demands by transport workers claiming extra money for additional work during the Games and Paralympics.
First it was mainline trains threatened by strike action over Olympic bonus payments and then Tube workers threatened to walk out if they didn't get extra money.
Using industrial muscle they have all forced additional payments.
Now union barons are planning the same tactics for bike staff.
The RMT union confirmed today it is to ballot members of the Barclays Cycle Hire scheme who service and look after the 5,000 bikes and 300 "docking stations."
Bob Crow, the RMT leader, said: "We are sending out the clearest message to Serco Barclays, the scheme operators, by calling this ballot that we are serious about this fight for justice on pay and working conditions and we remain available for talks."
He said staff would be facing an "increasing workload this summer as we head towards the Olympics."
Mr Crow said the cycle scheme "is now a valuable part of our transport system and the staff should be valued as such."
A date for the ballot to begin has not yet been set. The union refused to say how many staff are involved.
Mainline train and Network Rail staff involved with the Olympics are to receive upwards of £500 each for extra work; Tube workers will get £850 each in a deal agreed this week.
Tube train drivers, however, are easily at the top of the Games bonus league and will get anything from £1,000 to several thousand pounds to work changed and extended shifts during the Olympics and Paralympic Games.
A TfL spokesman said: “This is a matter between Serco and the RMT, who we would urge to resolve any issues through constructive discussion.”
A Serco spokesman said: "Serco has sought to maintain at all times a productive and mutually respectful relationship with our staff on the Barclays Cycle Hire Scheme.
"We have an existing voluntary recognition agreement with the Community Trade Union and we are holding a meeting on 12 June to discuss working arrangements for the Olympics.
"Serco has been in consultation with our staff with regard to changes to working conditions and workload and shift patterns have been changed as a result.
"All proposed future changes would be subject to consultation, both formally through dialogue with the Community Trade Union, and informally through internal staff communication and management engagement.
"The RMT is not a recognised union at Barclays Cycle Hire Scheme. The RMT formally withdrew their application to be recognised on this contract through the Central Arbitration Committee on 24 May."
