Owing to their intriguing characteristics, the ongoing pursuit of emerging mono-elemental two-dimensional (2D) nanosheets beyond graphene is an exciting research area for next-generation applications. Herein, we demonstrate that highly crystalline 2D boron (B) nanosheets can be efficiently synthesized by employing a modified liquid phase exfoliation method. Moreover, carrier dynamics has been systematically investigated by using femtosecond time-resolved transient absorption spectroscopy, demonstrating an ultrafast recovery speed during carrier transfer. Based on these results, the optoelectronic performance of the as-synthesized 2D B nanosheets has been investigated by applying them in photoelectrochemical (PEC)-type and field effect transistor (FET)-type photodetectors. The experimental results revealed that the as-fabricated PEC device not only exhibited a favourable self-powered capability, but also a high photoresponsivity of 2.9-91.7 μA W-1 in the UV region. Besides, the FET device also exhibited a tunable photoresponsivity in the range of 174-281.3 μA W-1 under the irradiation of excited light at 405 nm. We strongly believe that the current work shall pave the path for successful utilization of 2D B nanosheets in electronic and optoelectronic devices. Moreover, the proposed method can be utilized to explore other mono-elemental 2D nanomaterials.