Stereolithography (SL) is one of the rapid prototyping (RP) systems that use liquid photopolymer resin as the raw material for building prototypes. The photopolymer type of the RP system employs lasers to selectively expose the surface of the liquid resin. The absorbance of energy leads to photo-polymerization that transfers the liquid resin into solid. Subsequently, the phenomenon of volume shrinkage is unavoidable, and the curl distortion changes with the different laser scan paths, even affecting the geometric profile of the final-parts. The volume shrinkage and curl distortion are the major causes that lead to poor accuracy of the built prototype. In order to understand and improve the curl distortion and the geometric profile, so as to find a simple and suitable laser scan path. This paper first of all uses simulation and experiment to explore the deformation and shrinkage during the process of photo-polymerization while the liquid resin uses a laser beam to carry out single line scanning or single layer scanning in liquid free surface, and further understands the final change of geometric profile. Secondly, it investigates into the curl distortion and changes of geometric profile occurred in the three-dimensional part by different scan paths. Finally, a simple, proper, and effective laser scan path planning is suggested to decrease the curl distortion, and promote the dimension accuracy and the profile of the final-parts. Besides, this paper also mentions the feasibility of multi-optical processing.