Neolithic inhabitants at Çatalhöyük used volcanic obsidian to make tools and mirrors (shown here). New data connecting Hasan Dag to the Çatalhöyük mural contextualizes the important lithic industry. Photo: Catalhoyuk Research Project
Admittedly this doesn't look all that impressive now, but I've also seen one (in a photo, in a book, alas, couldn't find it online) about 7000 years old, obsidian, and carved with a handle, looks like something one might buy today.
