I have some back issues of the main Books of Magic series, however I don't have the Neil Gaiman mini-series that preceded it.
Does reading the mini-series first add value to the main series?
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Since Neil Gaiman created the character and explains the "magic" in the DC Universe, I would say yes, it adds immense value. The John Boltan (and others) art is also a nice addition. I would also read the 4-issue mini-series The Trenchcoat Brigade at some point as it revisits the original mini-series. It's not as important when you read the 2nd mini, though, if memory serves. It's a self-contained series and not necessarily between certain issues of the on-going series.