Two model biomimetic systems, ethyl sinapate (ES) and its symmetrical analogue, diethyl 2-(4-hydroxy-3,5-dimethoxybenzylidene)malonate (or diethyl sinapate, DES), are stripped to their core fundamentals through gas-phase spectroscopy to understand the underlying photophysics of photothermal materials. Following photoexcitation to the optically bright S 1 (ππ*) state, DES is found to repopulate the electronic ground state over 3 orders of magnitude quicker than its nonsymmetrical counterpart, ES. Our XMS-CASPT2 calculations shed light on the experimental results, revealing crucial differences in the potential energy surfaces and conical intersection topography between ES and DES. From this work, a peaked conical intersection, seen for DES, shows vital importance for the nonradiative ground-state recovery of photothermal materials. This fundamental comparative study highlights the potential impact that symmetrical substitution can have on the photodynamics of sinapate esters, providing a blueprint for future advancement in photothermal technology.