Two of the highest achieving Australians in football are set to face off in a titanic debut Women's Champions League match for De Vanna, as Fiorentina take on Women's Super League champions Arsenal.

It will be De Vanna's debut for le Viola, with the Florentines set to take on the Gunners 3am this Friday, AEST.

Arsenal have already kicked off their WSL campaign with a 2-1 win over Jacynta Galabadaarachchi's West Ham (the Aussie connections coming thick and fast) but are still recovering from an awful run of pre-season losses.

The always confident De Vanna will be hoping to nip any momentum in the bud. The two have had a steely relationship at times over the years, harking back to Montemurro's successful W-League coaching days.