The invention discloses a preparation method and application of an orthorhombic-phase two-dimensional layered SiP single crystal and a film. The method comprises the following steps that 1, Si, P and Sn are weighed, Sn serves as a metal fluxing agent, then the three raw materials are put in a quartz tube, and after the quartz tube is vacuumized, sintering is conducted for sealing the quartz tube; 2, the quartz tube is put in a heating furnace, a stage temperature rise program is adopted, and Si and P are in a sufficient combination reaction; 3, after o-SiP nucleates and grows, the quartz tube is taken out of a hearth and inverted, and an o-SiP single crystal and the metal fluxing agent Sn are separated; 4, the quartz tube is opened, the material block is taken out, the fluxing agent Sn adhering to the surface of o-SiP is removed, the material block is cleaned up, and a flaky o-SiP crystal is obtained; 5, the o-SiP crystal is immersed in an NaoH solution, sediment is extracted out after ultrasonic treatment, and the sediment is cleaned to obtain the orthorhombic-phase two-dimensional layered SiP single-crystal nano-film with a large size and high quality. The film can be applied to a saturable absorber for modulation of lasers and can be used for passive mode locking of an ultrashort pulse laser and manufacturing of photoelectronic devices or radiation detectors or solar cells.