I think your question is a bit contradicting. Most people would agree that when something is not worth it, you dont/shouldnt pay for it. Its the principle capitalism uses to maximise profit. What I guess you mean is what are things that we pay more for instead of using cheap alternatives? If so, then my answer is basically everything that I dont buy second hand.

Food for better quality, taste and climate footprint (Bio quality).
Fruit juice, there is an insane difference in taste.
Electronics for usability, longevity (less trash) and of course quality.
Furniture for longevity, reciclability.
Tooth paste, creams, medicine, anything that goes inside my body for obvious reasons. Important to note that some stuff (esp. medicine) is exactly the same just 10 times more expensive because of brand names. In that case I dont bother.

Recent examples:

• Fairphone (totally worth it when considering I can just replace parts instead of buying a whole new phone every 4 or so years, will easily last me the promised 8 years of promised software updates and probably longer)\
• Washing machine and dryer from miele for 1000€ each. They feel so high quality, pleasant to use and will probably last 30 years.