I don't know about Australia or other insurance companies, but whenever I've asked my homeowner's insurance company they are adamant that my books are covered under my general policy. I don't need a special rider like with jewelry or furs or a gun collection. I've photographed and catalogued everything myself so I'll have a easier time with a claim if it ever comes to that. So in essence I've done my own valuation, and as long as I can back that up my insurance company will accept that.
If you don't have a homeowner's policy, I'm not sure what advice I could give. Maybe Lloyds if you've got an expensive collection?
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