If you can find linen/silk blend garments they are awesome and 100% natural. I once found such a shirt in a thrift store and it lasted me for years. But there's a reason I only ever owned that one shirt, and as you might guess the reason is the price. A decent quality linen/silk shirt can easily cost several hundred dollars. At a guess, I'd estimate that the same quality shirt in linen/rayon would be less than 1/3 the cost.

If cost is not an obstacle, linen/silk is fantastic. If you're not independently wealthy, stick with linen/rayon. Pure linen is hard to find for reason--it's not as good as the blends.