Her clothes are still on the hangers, and somebody has to decide which ones go to a donation truck and which ones stay in the house. Before you book a pickup, settle what they will take, who will be home, and what paper you get when they leave. A donation pickup is easy to schedule and hard to undo, so the decisions come first.
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Sort into three piles before anyone calls
Make three piles on the bed or the spare room floor: keep, give, and not yet. Keep is for the things he or you want to see again. Give is for the clothes that are clean, usable, and not special to anyone. Not yet is for the pieces that need another week. Let him take the lead on the first pile. He may want to keep the coat she hung by the back door, and he may want to give away the rest without looking. Both are fine.
Check what the charity takes
Ask each group whether they accept shoes, coats, bedding, and small household items, and whether they take anything with stains, tears, or pet hair. Some pickups only take clothes in bags, and some will take a whole dresser or a bookshelf. Ask whether they prefer boxes or bags, and whether the clothes should be folded or hung. A group that collects bagged items from the porch is easier than one that wants you to haul everything to a drop-off on a weekday afternoon.
Ask who carries it and how
Find out whether the crew comes into the house or only to the curb or porch. Ask whether they carry items down stairs, whether they need the door unlocked, and whether they can come at a time when you or he will be home. If he would rather not watch, ask whether he can wait in another room. Ask whether there is a minimum load, and whether a small pickup is possible if you only have a few bags.
Ask what paper you get back
Ask whether they give a written receipt listing what was taken, and whether you can keep it in the family folder. A short list of what left the house is worth having for your own records. If questions come up about what a donation means for taxes or for anything legal, check with your own accountant or advisor, because the charity can describe what it provides but cannot advise you on what it means for you.
What to do tonight
Start the three piles on one bed, not the whole room. Put a note on the top of the give pile saying when you plan to call. Write down the two or three groups you are considering, what each one takes, and whether they come into the house. Then sleep on it. The closet will still be there in the morning, and so will the coat by the back door, and nothing has to leave tonight.