In a statement, the GLA said: "Allegations have been brought to the attention of the monitoring officer that Boris Johnson maintained a friendship with Jennifer Arcuri and as a result of that friendship allowed Ms Arcuri to participate in trade missions and receive sponsorship monies in circumstances when she and her companies could not have expected otherwise to receive those benefits.
"A 'conduct matter' exists where there is information that indicates that a criminal offence may have been committed.
It does not mean that this is proved in any way.
The issue has been referred to the IOPC because as mayor Mr Johnson held a post equivalent to a police and crime commissioner.
The move by the GLA to refer the Prime Minister to the Independent Office for Police Conduct has met with anger from No 10.
A senior Government source said it was "a politically motivated attack" and that the timing - on the eve of the Conservative Party conference - was "overtly political".
"No evidence of any allegations has been provided by the monitoring officer nor was the PM given any opportunity to respond to the monitoring officer prior to the publishing of a press release late on a Friday night," the source said.
"The public and media will rightly see through such a nakedly political put-up job."