Cross-linked starch nanocapsules (NCs) were synthesized by interfacial polymerization carried out using the inverse mini-emulsion technique. 2,4-toluene diisocyanate (TDI) was used as the cross-linker. The influence of TDI concentrations on the polymeric shell, particle size, and encapsulation efficiency of a hydrophilic dye, sulforhodamine 101 (SR 101), was investigated by Fourier transform infrared (FT-IR) spectroscopy, dynamic light scattering (DLS), and fluorescence measurements, respectively. The final NC morphology was confirmed by scanning electron microscopy. The leakage of SR 101 through the shell of NCs was monitored at 37 °C for seven days, and afterwards the NCs were redispersed in water. Depending on cross-linker content, permeable and impermeable NCs shell could be designed. Enzyme-triggered release of SR 101 through impermeable NC shells was investigated using UV spectroscopy with different α-amylase concentrations. Impermeable NCs shell were able to release their cargo upon addition of amylase, being suitable for a drug delivery system of hydrophilic compounds.