This study of the photodissociation of dimethyl sulfide at λ = 227.5 nm demonstrates the opportunities (and some of the challenges) of product detection using vacuum ultraviolet photoionization combined with recently developed multi-mass imaging methods. The capability of imaging different charged products simultaneously allows determination of the primary fragmentation dynamics through, for example, product fragment momentum and angular distribution matching and reveals potential complications from dissociative ionization, product alignment-dependent photoionization probabilities, and the effects of space charging.