Layers, layers, layers.
Underneath it all, women should wear a sports bra. Both men and women may experience painful chafing - apply petroleum jelly if you do not wear a bra. Spandex running shorts are a great idea for both sexes to prevent chafing in the upper thigh area.
Your inner layer should be of a wicking fabric such as polypropylene or coolmax. But I know you - you will wear the free t-shirt they give you for registering for the walk, or one you have from last year. That's fine, although cotton shirts will retain sweat and moisture during the event and you will end up feeling damp and clammy.
In most climates you will want a windproof, water resistant outer layer - a jacket or windbreaker. One with a rain hood is an excellent idea - umbrellas end up poking other walkers or being a chore to carry.
In cold climates, you should wear an insulating layer between your t-shirt and your jacket. Microfleece is an excellent choice. A wool shirt is OK. Sweatshirts end up being - sweaty. You will usually get pretty warm after the first few minutes walking and so will be shedding layers.
If it isn't good weather for shorts, then select comfortable pants that move easily with you. Many folks will wear jeans, but they are a poor choice -made of heavy, water absorbant fabric. But if your jeans are simply your most comfortable pants, then go for it.
In any weather, a hat to keep your head warm or the sun off your scalp is a requirement.
Know your event - at some of them folks dress up in zany costumes. If you do that, keep it simple enough to walk in and have fun.
Most charity events are short enough that you won't need to carry much. Ditch the purse and dig out a waistpack in which to carry your keys, identification, and other essentials
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