It depends on the catalogue you use, but generally speaking: no. catalogue values are useful to compare or exchange stamps based on their value. Normally, there is no need to pay full c.v. for stamps. When valueing collections it all depends on the special items that are in it (or not). "normal" collections are often worth as much as the album they are placed in.
My personal experience is that there is no correlation between catalog value and whole sale or retail value that's depenable. The basic valuation principle remains a stamp(s) are worth what someone is willing to pay.
There are no general rules, but in my experience you should probably expect to pay 50% to 80% of current Scott's value for run of the mill F-VF or VF stamps. You could expect to get 25% to 30% when selling them. That's when working with a dealer or through an auction.
Better, rarer stamps can cost you full Scott or better. "Graded" (PSE, etc.) material can cost you hundreds of dollars for a stamp that otherwise would cost you a buck or so.
What it really comes down to is that a stamp is worth what you are willing to pay for it or willing to sell it for.
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