Single-layer single-crystalline SnSe nano-sheet with four-atomic thickness of similar to 1.0 nm and lateral size of similar to 300 nm is presented here by using a one-pot synthetic method. It is found that 1,10-phenanthroline plays an important role in determining the morphology of the SnSe product as three-dimensional SnSe nanoflowers are obtained in the absence of 1,10-phenanthroline while keeping other reaction parameters the same. The evolution process study discloses that single-crystalline nanosheets are obtained from the coalescence of the SnSe nucleus in an orientated attachment mechanism. Band gap determination and optoelectronic test based on hybrid films of SnSe and poly(3-hexylthiophene) indicate the great potential of the ultrathin SnSe nanosheets in photodector and photovoltaic, and so forth.