The Italians host the first leg at their cavernous, crumbling caulderon of a ground the Stadio San Paolo which is one of the toughest places for any side to visit in this part of the world. Indeed Napoli have only lost two Serie A matches at home in their last 29 fixtures.
Last season Juventus ran away with the Scudetto but La Vecchia Signora went down 2-0 in Naples, just a indication of the size of the task facing Athletic Bilbao on Tuesday night.
Paddy Power price the Basques at 7/2 (4.50) while Napoli are offered at 3/4 (1.75) and the draw can be backed at 13/5 (3.60).
That Athletic are even in contention for a place in the group stages of the Champions League is down almost solely to their home form last season.
On the road they were patchy winning just seven of their 19 away matches in La Liga, and having sold their best player in Ander Herrera to Manchester United, overcoming a strong Napoli side in Naples is a big ask.
Rafa Benitez's side have been in strong form in pre-season beating Greek Side PAOK and as well as Barcelona whilst narrowly losing to Ligue 1 champions Paris Saint-Germain.
Napoli have goals in them, from all over the pitch too, something that is sadly lacking from Athletic's squad with their main striker Artiz Aduriz unproven at European level and new signing Borja Viguera making a massive step up from the Spanish second division.
All this means that backing the hosts in some way makes sense and the price of 5/6 (1.83) for them to score over 1.5 goals looks appealing.
This bet has paid out in eight of their last 11 competitive games at home and with Atheltic only keeping five clean sheets in 21 competitive away fixtures last season, it has an excellent chance of providing us with some profit once again.
|Napoli to score over 1.5 goals at 5/6 (1.83) for a 2.5pt stake with Paddy Power|
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Phil Kitromilides is a sports journalist and TV presenter in Madrid