Discworld is a series. But, each book is a separate story. However, there are recurring characters, and things mentioned in later books that you might not understand all that well if you didn't read the earlier books. So while yes, you could read Discworld books out of order, you'll find much more enjoyment overall reading them in published order.
Now as to the Marlowe books, do they have any sort of references to earlier books? Do they build upon information in earlier books? Are there recurring characters from earlier books (other than Marlowe)? Do we get to know Marlowe better as the books go along in order? if yes, is answered to even one of those questions, then they are definitely books in a series.
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