With continuous shrinking of critical dimension (CD) and the application of immersion lithography system to technology nodes 22nm and beyond, the vector nature of electromagnetic fields propagating from mask to wafer plane cannot be ignored, rendering mask synthesis under scalar imaging model inadequate. In this paper, we develop a level-set based optimization framework for mask synthesis with a vector imaging model. The forward model of vector image formation is established, and then the photomask synthesis is addressed as an inverse imaging problem whose variational level-set reformulation is represented by a stable time-dependent model, which is solved by employing conjugate gradient methods of the cost function and readily available finite-difference schemes. Experimental results demonstrate pronounced performance in terms of pattern fidelity and edge placement error, together with notable computation acceleration and better convergence performance.