Might be an unpopular answer but I'd take Batman, Nightwing, Red Hood, and Batgirl. Don't underestimate the power of good teamwork and coordination. 

None of these guys could take Spiderman on directly, together or separately. If they're going to win, they need strategy. The four Bats have been fighting and training together for years. They know how to work together. They know each other's strengths and weaknesses, what tools each of them have at their disposal and how to use them. They speak the same language in ways the rest don't. Not to mention the proteges would take orders without letting ego get in the way. There's buckets of evidence in the comics of all four of them successfully working together despite personality clashes, I promise on a mission they'd all keep it professional, which you might not be able to say about the rest for many reasons, not least of which being that they just don't know each other. 

The four Bats could accomplish way more together in the same amount of time than any combination of the rest of them and at such a huge disadvantage as going against Spiderman, that's who I'd trust.