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ECommerce in simple language is buying stuff online. You must have used Amazon or eBay or website of any company (electronics, merchandise, etc) to buy stuff online. These buying and selling things online is called eCommerce.
Typically in eCommerce there will be a website of a company where people can visit either as a guest or as a registered user and then add items to your cart. Then promotions are applied if any then you have to checkout / pay for items in your cart and then submit your order.
This is how eCommerce works.