Different submicellar solubilization mechanisms of two systems, Triton X-100 (TX-100)/tetradecane and sodium dodecyl sulfate (SDS)/butyl methacrylate, are revealed on the molecular scale by ¹H NMR spectroscopy and 2D diffusion ordered spectroscopy (DOSY). It is evident that the apparent solubilities of both tetradecane and butyl methacrylate are enhanced, even at much lower surfactant concentrations than the CMCs. Solubilized solutes also contribute to the early formation of surfactant micelles. In general, the molar solubilization ratios (MSRs) of both solutes linearly increase as the surfactant concentrations increase. However, variations in MSRs of the two systems are different below and above the CMC, which is probably related to the different solubilization mechanisms. For TX-100/tetradecane, as the TX-100 concentration increases, the tetradecane resonance in the independent state transforms into that of the aggregated state and the corresponding evolution of diffusions is shown in the 2D DOSY spectra. These results demonstrate that below the CMC, tetradecane is first solubilized in TX-100 solutions, and then solubilized in TX-100 micelles above the CMC. For SDS/butyl methacrylate, the appearance of oligomeric SDS resonances below the CMC indicates that butyl methacrylate is partially solubilized in SDS oligomers. Then, when the CMC is reached, the dominant, monomeric SDS molecules aggregate into oligomers, and the similar diffusivity trend of butyl methacrylate with that of SDS indicates that a proportion of butyl methacrylate molecules are solubilized in it. Finally, the fusion of SDS resonances in the two states and the tendency of co-diffusion of SDS and butyl methacrylate indicate that all the SDS molecules gradually aggregate into micelles, and almost all the butyl methacrylate molecules are solubilized in them. In conclusion, above the CMCs, the solubilization manners of these two systems are similar. However, they are different below CMCs. The solubilization of tetradecane by TX-100 is driven by the intermolecular hydrophobic interaction, i.e., molecular-pair formation. However, the polar interaction between functional groups of butyl methacrylate and the polar head of SDS contributes to the solubilization of butyl methacrylate. The different submicellar solubilization mechanisms are mainly caused by the different properties of solutes and surfactants, which also results in different MSRs and solubilization sites in the micelles.