Owing to its anisotropic optical and electrical properties,rhenium diselenide (ReSe2) has gered considerable attention recently as a candidate material for polarization-sensitive photodetectors.However,the direct and controllable synthesis of large-sized ReSe2 with a uniform thickness is still a great challenge.Herein,we have refined the synthesis method to obtain uniform monolayer ReSe2 flakes with a size of up to ～ 106 μm on sapphire via an ambient-pressure chemical vapor deposition technique using Na promoter from sodium chloride.Interestingly,optical pump-probe spectroscopy revealed a fast switching from saturable absorption (SA)to absorption enhancement (AE) in subpicosecond time scale,followed by a slower decay induced by exciton recombination.Furthermore,both AE and SA signals exhibited clear angular dependence with a periodicity of 180°,which reflected the dichroism in nonlinear absorption dynamics.In addition,the photocarrier dynamics including free-carrier transport and subpicosecond relaxation due to exciton formation or surface trapping was probed using time resolved terahertz spectroscopy.We believe that our study serves as a reference for atomically controlled synthesis of large-sized ReSe2 and provides useful insights on its optoelectronic properties for novel device applications.