This collects issues from Amazing Spider-man ( #519-528) as well as issues from Friendly Neighborhood Spider-man (#1-4) and Marvel Knights Spider-man(#19-22). These last two series are included because of a crossover event( "The Other") that was told continuously through these three titles. These collections live up to the "ultimate collection" tag, because they're very chunky. If you are interested in collection Straczynski's complete run (he's often described as being one of the best Amazing Spider-man writers) I would suggest these collections. Volume five is heavily out of print but the first four are relatively easy to find cheaply on Amazon.
Volume Four picks up where Volume Three left off: with Aunt May's house completely destroyed. This deeply rattles Peter Parker because this destruction happened not because of Spider-man's mistakes but of his own. There is a very emotional moment between Aunt May and Peter as they go through the remains of their home. Wondering where they will live now, Tony Stark quickly offers them housing in the Avengers Tower. So throughout the issues we get to see Luke Cage, Spider-woman, Wolverine, Jarvis, Captain America and Iron Man. I wish we could have seen more members of the Avengers and having more of the team dynamic, because I felt that Peter rarely interacted with them as a team but to be fair this isn't an Avengers title.
The first story arc involves Hydra. Apparently around this time in Marvel's main continuity Hydra is a criminal organization that is mostly filled with gagsters, but now the true Hydra members have resurface and taken over to restore Hydra to it's proper glory. After a run in with with clones of Thor, Captain America, Hawk Eye and Iron Man with poorly duplicated powers, Spider-man realizes that there is more going on that meets the eye. This is a typical "superhero" story. Bad guys have an evil plan. Superhero tries to stop them. Bad guys execute the plan and the superhero seems to fail, but redeems himself at the end. It's alright.
On the other hand "The Other" which is the second story arc in this volume is amazing. Throughout this run, Straczynski brings up the notion that Spider-man's powers came from the spider that bite Peter and not from radiation or Oz formula. This arc is called the "The Other" because it brings up the idea that Peter Parker has two sides: his human side and his spider side, but he has never truly embraced his spider side because of his fear of leaving his human side. Peter Parker is dying. It never truly says what he has but it's implied that it's a form of cancer. It's interesting to see how this disease was foreshadowed in the previous arc. One of the problems I do have with it is that it has a slow beginning and it drags on in the middle with the fighting and the ending seems rushed. The best part are the heart felt moments with Peter Parker and MJ (who are married) and you can see why their relationship works. Aunt May also has some very deep conversations with Peter and various other members of the Avengers, which I enjoyed.
Ultimately, I give this collection three stars. The first arc was two stars. The second arc was four stars. So I think three stars is pretty fair.