Methacrolein oxide (MACR-OO), the isopropenyl substituted Criegee intermediate (CI), is one product of isoprene ozonolysis. In this work, we report MACR-OO's photo-isomerization paths with electronic structure calculation at the CASSCF and MS-CASPT2 levels and trajectory surface-hopping (TSH) nonadiabatic dynamics simulation at the CASSCF level. Our calculated results show that the ring-closure is the dominant photo-induced unimolecular isomerization of MACR-OO in the S1 state. In addition, a new photo-induced ring-closure to heterocyclopentane dioxole in syn_syn-MACR-OO is found. The findings of MACR-OO are expected to deepen the understanding of the substituted CIs and their photochemistry.