It seems that occasionally my friends and I have issues connecting with each other. I'm assuming this is a firewall/router issue, although it could be something else. Under Network Settings in the game, I have it set to 'Friends Only' so it shouldn't be an issue with my game settings.
Borderlands – What ports do I need open to host a game
borderlands-2pc
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Best Answer
Borderlands 2 uses steamworks, and according to Chrisf they don't use any other special ports, so the standard steam answers apply.
Source
Steam Client
Dedicated or Listen Servers
Steamworks P2P Networking and Steam Voice Chat
Also, there are several ISPs which block ports required for the proper operation of Steam and Steam games:
Furthermore, Steam has their own connectivity support doc with the basic check your firewall, av software, etc. that you could try here.
The only interesting thing I see on it is starting steam with -tcp to force it to use all TCP ports instead of UDP, if that's messing something up on your end.