The supercritical CO2-based decaffeination (SCD) method can be used to prepare decaffeinated tea, but its overall effect on the phytochemicals, volatiles, and sensory qualities of green and black teas is still unclear, and its suitability to prepare decaffeinated green and black teas still needs to be compared. This study revealed the effect of SCD on phytochemicals, volatiles, and sensory qualities in black and green tea prepared from the same tea leaves, and compared the suitability of preparing decaffeinated green and black teas using SCD. The results showed that the SCD could remove 98.2 and 97.1% of the caffeine in green and black tea, respectively. However, it can cause further losses of phytochemicals in green and black teas, specifically the loss of epigallocatechin gallate, epigallocatechin, epicatechin gallate, and gallocatechin gallate in green tea and the loss of theanine and arginine in green and black teas. After the decaffeination, both green and black teas lost some volatiles but also generated new volatiles. Especially, the fruit/flower-like aroma, ocimene, linalyl acetate, geranyl acetate, and D-limonene, were generated in the decaffeinated black tea, while herbal/green-like aroma, β-cyclocitral, 2-ethylhexanol, and safranal, were generated in the decaffeinated green tea. The overall acceptance of decaffeinated green tea decreased due to the substantial reduction in bitterness and astringency, while the overall acceptance of decaffeinated black tea significantly increased. Therefore, SCD is more suitable for the preparation of decaffeinated black tea.