The bill will link to the expense account that you have selected under 'Category' on the 'Category details' line of the bill. Please not if you're running the PL report on a cash basis this will only show bills that have been marked as paid.
If you're entering items on the 'Item details' line of the bill instead of 'Category details', then the bill will post to the expense account that is selected on the product/service you have selected here - you can check this account by going to Sales > Products & services > Select 'Edit' against the product or service used on the bill > Scroll to 'Expense account' on the panel that appears on the right.
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