As a parameter important ballistic, the research about polygonal and grooved barrels’ behavior has not been widely carried out. The pressures, velocities, stresses, deformations, and strains generated by the firing of 9 mm × 19 mm ammunition in weapons with polygonal barrels are analyzed numerically and experimentally, compared with those generated in pistols with grooved barrels. The Finite Element Method with equal boundary and loading conditions was used in both types of guns, specifying the actual materials of the projectile and the barrels. Subsequently, experimental tests were carried out on various weapons with 9 mm ammunitions of 115, 122, and 124 gr. The results show that the 9 mm bullet fired in a polygonal barrel undergoes a maximum deformation towards its exterior of 0.178 mm and interior of 0.158 mm, with stress up to 295.85 MPa. Compared with 0.025 mm maximum external deformation and 0.112 mm internal deformation of 9 mm projectiles fired in a grooved barrel, with stress up to 269.79 MPa. The deformation in the polygonal barrel is in a greater area, but the rifling impression left is less deep, making its identification more difficult. Although there are differences in the stresses and strains obtained, similar velocity and pressure parameters are achieved in the two types of barrels. This has application in the development and standardization of new kinds of barrels and weapons.