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Lightly grease the inside of a 4- to 6-quart slow cooker with butter or cooking spray to help prevent sticking and make cleanup easier.
Peel the potatoes and slice them into thin rounds, about 1/8–1/4 inch thick. The more evenly you slice, the more evenly they’ll cook; a sharp knife or mandoline works well here.
In a medium bowl, whisk together the condensed cream of mushroom soup, milk, salt, and pepper until smooth and well combined. This creates the creamy sauce that will coat the potatoes and ham as they cook.
Layer about half of the sliced potatoes evenly in the bottom of the slow cooker. Scatter half of the diced ham over the potatoes in an even layer.
Repeat with the remaining potatoes and then the remaining ham, creating simple, even layers so the sauce can seep through.
Slowly pour the cream of mushroom mixture evenly over the top of the layered potatoes and ham, making sure to cover as much of the surface as possible. Gently tap the slow cooker on the counter or use the back of a spoon to nudge the top layer so the sauce settles down between the slices.
Cover the slow cooker with the lid and cook on LOW for 6 to 7 hours, or on HIGH for 3 to 4 hours, until the potatoes are very tender when pierced with a fork and the sauce is bubbling and thickened around the edges.
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Once done, turn the slow cooker to WARM and let the dish sit, covered, for about 10 to 15 minutes. This brief rest helps the sauce thicken slightly and makes it easier to scoop neat portions.
Taste and adjust seasoning with a pinch more salt or pepper if needed. Serve the scalloped potatoes and ham hot, straight from the slow cooker.
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