Coherent optical dressing of quantum materials offers technological advantages to control their electronic properties, such as the electronic valley degree of freedom in monolayer transition metal dichalcogenides (TMDs). Here, we observe a new type of optical Stark effect in monolayer WS2, one that is mediated by intervalley biexcitons under the blue-detuned driving with circularly polarized light. We found that such helical optical driving not only induces an exciton energy downshift at the excitation valley, but also causes an anomalous energy upshift at the opposite valley, which is normally forbidden by the exciton selection rules but now made accessible through the intervalley biexcitons. These findings reveal the critical, but hitherto neglected, role of biexcitons to couple the two seemingly independent valleys, and to enhance the optical control in valleytronics.Keywords: WS2, valley, biexciton, blue detuned, optical Stark effect, ultrafast opticsMonolayer TMDs host tightly-bound excitons in two degenerate but inequivalent valleys (K and K ), which can be selectively photoexcited using left (σ − ) or right (σ + ) circularly polarized light (Fig 1a) [1-4]. The energy levels of these excitons can be tuned optically in a valley-selective manner by means of the optical Stark effect [5,6]. Prior research has demonstrated that monolayer TMDs driven by below-resonance (red-detuned) circularly polarized light can exhibit an upshifted exciton level, either at the K or K valleys depending on the helicity, while keeping the opposite valley unchanged. This valley-specific phenomenon arises from the exciton state repulsion by the photon-dressed state in the same valley, a mechanism consistent with other optical Stark effects in solids [7,8].Despite much recent progress, a complete understanding of the optical Stark effect in monolayer TMDs is still lacking. First, the anticipated complementary effect of using above-resonance (blue-detuned) light to downshift the exciton level has not been demonstrated. This is challenging because the blue-detuned light excites real exciton population, which can easily obscure the optical Stark effect. Secondly, when the detuning is sufficiently small and comparable to the biexciton binding energy, the effect may involve a coherent formation of the recently identified intervalley biexcitons [9,10]. These biexcitons are expected to have profound contributions to the optical Stark effect, as indicated by earlier studies in semiconductor quantum wells [11,12]. Elucidating these processes is therefore crucial to investigate the role of intervalley biexcitons in monolayer TMDs in order to obtain a thorough understanding of the coherent lightmatter interactions in this system.In this letter, we explore the optical Stark effect using blue-detuned optical driving in monolayer TMD WS 2 . * gedik@mit.edu We found that by driving the system using intense laser pulses with blue-detuned and left circular polarization, we can lower the exciton energy at the K valley. In addition, as the driving pho...