First, we discuss the experimental characterization of HDMAPAN-(BF4)2 and the conjugate base, as well as the computational data to corroborate their conformation in solution, followed by the determination of the 𝑝𝐾 𝑎 . Then we explore the photoacidic character of HDMAPAN-(BF4)2 based on computational results for its most stable conformer. After confirming the photoacidity, we present a series of computational experiments to evidence the new photoacid mechanism through which HDMAPAN-(BF4)2 operates.