Herbal
An untested chemical that grows in the garden. Possibly not your garden.
It could be benificial – Aspirin is after all a cleaned up and tested version of what was previously a herbal remedy. It could be safe; at least it could be safe in the kind of doses suggested (everything is poisonous enough in high enough doses – even water).
But it has not been tested properly either for effectiveness, nor safety. And if it is effective, is it more effective than a placebo?
Chemical-Free
Another way of saying an empty bottle. If you shake your bottle and it rattles or gurgles, send it back as it's got chemicals in it.
Homeopathy
Expensive water.
In fact if there were any positive value to homeopathy, there would be no complaints of joint pain in hard water regions (calcium carbonate is supposedly a treatment for joint pain). And guess what? I get both hard water through my taps, and joint pain.
Natural
… as opposed to "man-made". Both are a means of production and neither means of production has any implications as to the effectiveness of a product.
However evolution does not tend to produce something whose sole purpose is to cure headaches; the willow tree evolved to have a nasty bitter tasting bark to discourage animals from eating its bark not to cure headaches. That was an accident. To treat a headache "naturally", you will need to find a willow tree, pull off a chunk of bark, grind it up, and eat it. A man-made pill labelled "Aspirin" is more readily available, safer (it only contains the chemical for the headache treatment), and is less damaging to those poor willow trees.
So in this case, "natural" is actually a bad thing.
Faith-Healing
Asking an imaginary friend for help. Frankly asking a real friend is just as likely to work, and any effectiveness is due to the placebo effect.
Acupuncture
If you want someone sticking pins in you to make a little wax figurine replica of you to say "Oww!" then by all means go ahead.