While click-to-release initiated the era of clinical translation of in vivo chemistry, it has not yet achieved what originally made the Tz/TCO IEDDA ligation one of the most appealing bioorthogonal reactions: exceptional click reactivity. This limitation is due to several mechanistic aspects that remain to be unraveled, along with the inherent trade-off between the IEDDA reactivity and the release efficiency of tetrazines. Hence, applications of Tz/TCO click-to-release are often restricted by limited reaction rates in the initial IEDDA step, or by incomplete and/or slow release. In our ongoing endeavor to tackle this challenge, we show herein that aryl-tetrazines, frequently used for rapid bioorthogonal ligation, can be transformed into advanced bioorthogonal scissors for efficient click-to-release. By incorporating OH functionalities as intramolecular proton-exchanging groups that direct and enhance post-click tautomerization and elimination, we obtained bishydroxyaryl-Tz that achieve near-complete release of the commonly applied cleavable trans-cyclooctenes rTCO and cTCO.