Atomically thin two-dimensional (2D) layered semiconductors such as transition metal dichalcogenides have attracted considerable attention due to their tunable band gap, intriguing spin-valley physics, piezoelectric effects and potential device applications. Here we study the electronic properties of a single layer WS1.4Se0.6 alloys. The electronic structure of this alloy, explored using angle resolved photoemission spectroscopy, shows a clear valence band structure anisotropy characterized by two paraboloids shifted in one direction of the k-space by a constant in-plane vector. This band splitting is a signature of a unidirectional Rashba spin splitting with a related giant Rashba parameter of 2.8 ± 0.7 eV Å. The combination of angle resolved photoemission spectroscopy with piezo force microscopy highlights the link between this giant unidirectional Rashba spin splitting and an in-plane polarization present in the alloy. These peculiar anisotropic properties of the WS1.4Se0.6 alloy can be related to local atomic orders induced during the growth process due the different size and electronegativity between S and Se atoms. This distorted crystal structure combined to the observed macroscopic tensile strain, as evidenced by photoluminescence, displays electric dipoles with a strong in-plane component, as shown by piezoelectric microscopy. The interplay between semiconducting properties, in-plane spontaneous polarization and giant out-of-plane Rashba spin-splitting in this 2D material has potential for a wide range of applications in next-generation electronics, piezotronics and spintronics devices.