Herein, the catalytic effects of aromatic amines with different structures on the room temperature curing of bisphenol E cyanate (BECy) have been studied using differential scanning calorimetry (DSC) and Fourier transform infrared (FT-IR) spectroscopy. Our results revealed that the mixed amine comprised of aniline and N,N-dimethyl-p-phenylenediamine (AN/NNDPA) bearing primary amino groups in its structure was a highly effective catalyst for the room temperature curing of cyanate esters. When the cyanate ester and mixed amine were combined at a molar ratio of 100:5 and cured at room temperature for 5 days, the curing degree of BECy resin reached 79.7%. The room temperature curing mechanism of the BECy-AN/NNDPA system was investigated using pyrolysis gas chromatography-mass spectrometry (PY GC-MS). Our results showed that the formation reactions of the intermediate structure and cyclotrimerization reactions occurred during the room-temperature curing process. The activation energies of BECy and different aromatic amine systems at different heating rates were determined using non-isothermal DSC. The results further demonstrated the catalytic effect of AN/NNDPA on the cyanate ester curing reaction. BECy-AN/NNDPA cured at room temperature has suitable heat resistance and a 5% weight loss temperature (Td5) of 361°C.