There are no USDA recommendations on the addition of fresh herbs to water bath canned fruit products. That said, it is most likely safe to do so unless you are adding so much basil you push the overall pH of the contents of your jar above 4.5, and that would take a lot of basil. If you put a basil leaf or two in your canned peaches it is very, very unlikely you will have any problems. If you are doing hot pack, you can flavor the syrup you pack the peaches in. Just swish a bouquet of basil leaves in the syrup, discard the basil, and continue with the syrup as described in your recipe. This technique works very well.
I am assuming you are hot packing your peaches before canning, and that is what you mean by poaching the peaches. I am overly cautious when it comes to adding anything outside prescribed methods. My recommendation is not to add basil. When you open the peaches add basil at that time it will be better because it will be fresher. Basil oil would even be tastier!
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