Wash and peel the peaches. To make peeling easier, blanch them in boiling water for 30 seconds, then transfer to an ice bath.
Slice the peaches into wedges or leave them in halves, depending on your preference. Remove the pits.
In a medium saucepan, combine the vinegar, water, sugar, cinnamon stick, cloves, star anise, ginger, peppercorns, and chilli peppers (if using).
Bring the mixture to a boil over medium heat, stirring until the sugar dissolves completely.
Reduce the heat and let the brine simmer for 5-10 minutes to allow the flavours to infuse.
Sterilize your canning jars and lids by boiling them in water for 10 minutes or running them through a dishwasher cycle.
Pack the peach slices or halves tightly into the sterilized jars.
Carefully pour the hot pickling brine over the peaches, ensuring they are fully submerged. Leave about ½ inch of headspace at the top of the jar.
Wipe the rims of the jars with a clean cloth to remove any spills.
Seal the jars with the lids and bands.
Let the jars cool to room temperature, then refrigerate. For longer storage, process the jars in a water bath canner for 10 minutes.
Let the pickled peaches sit for at least 24 hours (or up to a week) to allow the flavors to develop.
Serve as a condiment with roasted meats, cheese platters, or enjoy them on their own as a tangy-sweet treat.