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Not sure about the UK but where I live in the US there are small town /small city local papers. Look in the advertisement area and direct mail the companies or contact them by phone. If you mail them I would follow up with a phone call. You can also use your telephone directory/book. Or if you know of local stores etc that would be good candidates for websites you can contact them. Like I say, I don't know much about the UK but besides a big pond between us we can't be that much different :)
In your area too, there will be small shops, selling stuff.
Have you tried telling them the benefits of an email address. With that mail address, they can get a small website listing contact info (opening hours, tel/fax), or if they are specialised enough, they might even think about selling online.
I have had good results with local restaurants, and student associations (those drinking clubs, you know what I mean)..
Once they get the appetite, they'll need a bigger website, and counseling on how to oopimise that website to be found.
Go through the local directory like yellow pages or whatever and pick a business type in your area and call them all.
If they have an email address in there ad but no website these are grade A targets.
Call them. Don't email or write and don't waste money advertising unless you can do it on a larger scale. Just call them.
Ask for the owners name, and ask to talk to him. If the 'gate-keeper' gives you any grief, move on, no point wasting your time.
When you get to talk to them here's the pitch:
Hi, Ive just started a new business and am looking for some companies without websites to use as examples of my work. I don't do it for free, but if you like the other stuff I've done (send email) I'd be happy to do something for you for a seriously good rate providing that I can use your website as an example of my work in my portfolio.
They'll love it.
Just remember to not get frustrated or mad with the guys you can't get speak to. Don't argue with the secretary, just move on, there's loads of people to talk to.