Multi‐branched probes based on 2‐hydroxymethylene 8‐dimethylaminoquinoline (8‐DMAQ) and triphenylamine (TPA) have been synthesized and compared under UV and femtosecond near‐infrared two‐photon (2P) activation conditions. While octupolar ( 3 ) and quadrupolar ( 2 ) DMAQ derivatives showed superior ε and 2P absorption cross‐section ( σ 2 ) values relative to the dipolar ( 1 ) probe, the fragmentation efficiency exhibited an inverse correlation with the enhanced absorption. Compound 1 emerged as the most effective probe reported to date for the release of organic substrates under both UV and 2P activation conditions at wavelengths accessible to commercially available lasers, achieving a quantum yield ( Q ) of 12% with σ 2 = 86 GM and uncaging cross‐section δ u = 10.2 GM at 735 nm.