The dynamics of excited states in organic photosensitizers fundamentally determine the performance of clinical photodynamic therapy (PDT). Therefore, it is essential to deepen our understanding of the structure-dynamics relationship with aiming to manipulate excited states accordingly. However, the limited knowledge of excited-state dynamics in organic structures poses significant challenges to such rational manipulations. Our research addresses this gap by focusing on the structure-dynamics relationship in organic materials to enhance PDT performance. We utilized femtosecond transient absorption (fs-TA) spectroscopy to gain insights into excited-state dynamics. Our research on excited-state dynamics in organic molecules revealed that geometry-twisting greatly enhances intersystem crossing (ISC), providing a new way to develop organic materials with external stimuli-responsive reversible switching of ISC. This understanding of ISC can lead to the development of advanced photosensitizers for PDT.