A novel NMR approach for the study of gelation in flexible polymer systems is presented, and the data are compared to results from rheological and light scattering experiments. Proton multiple-quantum NMR, also applicable at low field and amenable to high-throughput experimentation, represents a simple and robust yet powerful method that allows one to detect the topological gel point, quantify the gelation kinetics, and characterize composition, microstructure, and dynamics of the forming and the final gel. Applications to end-linked and statistically cross-linked poly(dimethylsiloxane) chains in the bulk, as well as statistically cross-linked poly(styrene) chains in solution are presented, and good agreement as well as complementarity between the results from the different methods is found.