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This book is a a bit of a hodge-podge.
5 separate issues all tied together by the ongoing Civil War.
Out of the stories 3 are pretty good - Power-Man, Iron man & Spider-Woman but the Sentry one is a mess & the Captain America story, whilst fair enough is ruined by pretty poor artwork.
Each of the stories deal with how an individual character deals with the fallout of the Super-hero registration Act and because of this teh book is probably best read alongside the collected edition of Civil War (& it's assorted tie-in books). Without having the main story to give this book the appropriate context it falls down somewhat.
Bendis obviously knows what he's doing with Spider-Woman & Power man as these 2 tales are the stand-outs of the collection & bode well for their continuing adventures underneath this scribe.
Iron Man and Captain America have interesting tales that offer differing takes on the War as they show some of their reasons for taking opposing sides.
The Sentry story is unfortunately a waste of paper that contradicts other appearances.
However, if you're following the Captain America Series by Ed Brubaker or collecting the other Civil War titles then this book is a worthwhile addition to your collection.
If you're only reading the New Avengers then this book makes a bit of a startling jump compared to previous volumes (& will get worse as you move on to later stories).
If you're a casual reader there's better starting points to get to know the Avengers such as teh first volume of New Avengers or some of the early classic stuff by talent such as Stan Lee, Roger Stern & George Perez.