Frustrated Lewis pairs (FLPs) have been widely investigated as promising catalysts due to their metal-free feature and ability to activate small molecules. Over the last few years, the structure, dynamics and interactions between the Lewis centers and their effects on the reactivity with different substrates have been studied. Nuclear magnetic resonance (NMR) is a powerful tool in studying the reaction intermediates, kinetics and mechanism of frustrated Lewis pairs (FLPs). Various NMR experiments have been applied to precisely determine the association or cooperativity of FLPs and one or two-dimensional spectra were obtained. Herein, insights coming from NMR spectroscopy for FLPs are presented, the structure and reactivity of FLPs in solution are described, and their effects on the kinetics and mechanism of different substrates are also illustrated in this review.