The modulation of valley polarization in one single system is of important fundamental and practical importance in quantum information technology. Here, through the first-principles calculations, we identify single-layer TcIrGe2S6 as a tantalizing candidate for realizing the modulation of valley polarization. Arising from the combination of inversion symmetry breaking and intrinsic magnetic exchange interaction, single-layer TcIrGe2S6 exhibits spontaneous valley polarization. The value of valley polarization in the conduction band is 161 meV, favorable for achieving the intriguing anomalous valley Hall effect. Furthermore, single-layer TcIrGe2S6 possesses ferroelectric order. More remarkably, its ferroelectric and valley physics can be strongly coupled, namely, the valley properties can be switched off and on electrically. These findings not only provide a compelling candidate for two-dimensional valleytronic research but also open a new avenue for modulating valley physics.