You can't buy prescription medications on the Internet (in the States) without a prescription, whether it's for bio-identical or non-bio-identical hormones or any other non-hormonal medication. In reality, I suppose you could buy just about anything over the Internet, but then I would worry about the effectiveness and sterility of the medication.
However, all is not lost. Check out my website for my page directed at folks seeking free or low cost medical care & drugs (sorry but I can't seem to link properly w/live URLs). You might find some less expensive sources using that as a starting point. If you have insurance, ask for something like Vivelle Dot or Climara (not Climara Pro), and Prometrium (if you need a progestin) since these Big Pharma brands are typically covered by insurance as opposed to the compounded stuff. Good luck!
As an aside, I'm glad you asked about bio-identical rather than natural hormones. After all, not everything that's natural is good for us. Poison oak, anyone? And since when isn't a horse natural? I jest of course, but hopefully you understand my point. There are many bio-identical options available. And don't forget that in some situations, route of administration makes a tremendous difference (I think transdermal will prove to be safer than oral). In any case, what's most important is that you discuss your concerns with your family physician and seek his/her guidance to help you meet your needs. Again, good luck!
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