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I understand that there are a number of syndicates and that's the general rule for who will work for whom, but the mercenary warcasters don't list syndicates that I can tell.

I am wondering about how this is arranged in the Mercs book, so I can better understand it, and I am in particular curious about Ashlynn as a stand-alone warcaster. What kind of Mercenary army can she field? Anyone who will also work for Cygnar/Protectorate, or are there more restrictions? What about Boomhowler? Will he work for her?

Anyone who will work for Cygnar plus a couple of Cygnar units if you field her tier.

Go here to build a list for her as 'Ashlyn tier list' or 'Highborn Covenant'.

Is there a rule somewhere in the Mercs book? I'd hate to have to reference web sites just to build armies.

Yes the Mercenary book has the rules for building Mercenary 'Contract' and 'Theme' lists.

Her tier list is basically a Cygnar-lite army that you can do very interesting things with like putting a Mule on the UA for the gun mages. You can use any mercs with her that will work for Cygnar also.

She's a gateway drug for a Cygnar player to get into mercs and a Merc player to get into a Cygnar army.

The Contracts section of the Merc Book explains who can be fielded with who, as Spiggot said.