One important relaxation pathway for photo-excited five-membered heterocyclic organic molecules is ring-opening via a dissociative pi sigma* state. In this study, we investigate the influence of this pathway in furan and several hydrogenated and methylated derivatives by combining time-resolved photoelectron spectroscopy with time-dependent density functional theory and coupled cluster calculations. We find strong experimental evidence that the ring-opening channel is the major relaxation channel in furan, 2,3-dihydrofuran, and 2-methylfuran (2-MF). In 2,5-dimethylfuran (25-DMF), however, we observe that the molecules relax either via a pi 3s Rydberg state or through a direct return to the ground state by undergoing ring-puckering motions. From the supporting calculations, for 2-MF and 25-DMF, we predict that there is strong mixing between the pi sigma* state and the pi 3s Rydberg state along the ring opening pathway. However, in 25-DMF, no crossing between the pi sigma*/pi 3s state and the initially excited pi pi* state can be found along the ring opening coordinate, effectively blocking this channel.