AbstractA confined electronic system can host a wide variety of fascinating electronic, magnetic, valleytronic and photonic phenomena due to its reduced symmetry and quantum confinement effect. For the recently emerging one-dimensional van der Waals (1D vdW) materials with electrons confined in 1D sub-units, an enormous variety of intriguing physical properties and functionalities can be expected. Here, we demonstrate the coexistence of giant linear/nonlinear optical anisotropy and high emission yield in fibrous red phosphorus (FRP), an exotic 1D vdW semiconductor with quasi-flat bands and a sizeable bandgap in the visible spectral range. The degree of photoluminescence (third-order nonlinear) anisotropy can reach 90% (86%), comparable to the best performance achieved so far. Meanwhile, the photoluminescence (third-harmonic generation) intensity in 1D vdW FRP is strong, with quantum efficiency (third-order susceptibility) four (three) times larger than that in the most well-known 2D vdW materials (e.g., MoS₂). The concurrent realization of large linear/nonlinear optical anisotropy and emission intensity in 1D vdW FRP paves the way towards transforming the landscape of technological innovations in photonics and optoelectronics.