A series of pyrroloisoquinoline-1,3-diones has been synthesized using ruthenium(II) as the catalyst and oxygen as the oxidant in a straightforward manner. The reaction proceeds through a tandem C-C/C-N bond formation process between maleimides and ketoximes, providing a direct approach for the synthesis of the titled products. This operationally simple reaction procedure supplies suitable conditions for synthesizing diverse isoquinoline-based heterocycles with a range of functional groups in moderate to good yields and compatible with gram-scale synthesis. Furthermore, the compatibility of this reaction with oxygen as a green and environmentally friendly oxidant raises the importance of the present method.