The excited states of UV absorber, ethylhexyl methoxycrylene (EHMCR) have been studied through measurements of UV absorption, fluorescence, phosphorescence and electron paramagnetic resonance (EPR) spectra in ethanol. The energy levels of the lowest excited singlet (S1) and triplet (T1) states of EHMCR were determined. The energy levels of the S1 and T1 states of EHMCR are much lower than those of photolabile 4-tert-butyl-4′-methoxydibenzoylmethane. The energy levels of the S1 and T1 states of EHMCR are lower than those of octyl methoxycinnamate. The weak phosphorescence and EPR Bmin signals were observed and the lifetime was estimated to be 93 ms. These facts suggest that the significant proportion of the S1 molecules undergoes intersystem crossing to the T1 state, and the deactivation process from the T1 state is predominantly radiationless. The photostability of EHMCR arises from the 3ππ* character in the T1 state. The zero-field splitting (ZFS) parameter in the T1 state is D** = 0.113 cm−1.