A novel cross 1,3-dipolar cycloaddition between azomethine imines with in situ generated nitrile oxides has been developed. This is the first example of employing a reaction partner containing two heteroatoms in the [3+3] cycloaddition involving azomethine imines. This strategy not only provides structurally diverse N,O-heterocycles but also greatly enriches the chemistry of azomethine imines and nitrile oxides.