Is there Caffeine in Decaf Coffee? The answer is yes. Decaffeinated coffee has caffeine although negligible in brewed decaf coffee it can still be significant in decaf espresso. How is decaf coffee made? The decaffeination process does not remove caffeine entirely from the coffee bean and since the espresso-style brew has a higher rate of extraction due to grind size and temperature your best best is either hot decaffeinated coffee or cold brew decaffeinated coffee.