I send BioGroom an e-mail for free samples and never heard back from them. Next thing I know, I have a sticky on my door from FedEx saying they tried to deliver a package. Next day, I'm home and I get it and it has 4 bottles of 4 different samples. It was great!
I've also gotten coupons and free samples from Natural Balance. Usually if there's a company you like or want to try, you can find their e-mail on their website under "About Us" or "Contact Us", simply shoot them an e-mail asking for free samples they'll most likely send you some. Especially if they really want your business.