Thick-walled structures, such as marine engineering and rail transportation, are widely used in modern society. V-groove welding is a common welding method in thick structures. At the same time, the V-groove weld is also the area of a thick-walled structure in which defects are most easily formed. Laser-generated surface acoustic waves are a promising non-destructive testing method in most fields. This study examined the propagation characteristics of laser-generated surface acoustic waves in a V-groove weld. A two-dimensional finite element model with Q345 steel was constructed. A thermoelastic mechanism was adopted to generate the wave. The temperature and displacement fields were analyzed in detail. The results showed that wave transmission, reflection, and mode conversion are generated with an R wave at the junction, and the dispersion phenomenon of the R wave occurred in the welded area.