Advanced sources can now provide pulses of light and electrons with high energy and ultrashort duration. These sources provide new ways to measure dynamic chemical (electronic and geometric) structure that highlight previously hidden aspects of photochemical reactions. In this talk I will discuss two such techniques, focusing on extreme ultraviolet photoelectron spectroscopy and ultrafast electron diffraction measurements of CS2. The universal nature of both probes allows us to measure all parts of the reaction coordinate providing a detailed map of the structural (electronic and geometric) changes occurring. The measurements presented will highlight both the power of the techniques but also the challenges in interpreting the often complex and overlapping signals obtained.