We report 35 radial velocity measurements of HD 149026 taken with the Keck Telescope. Of these measurements, 15 were made during the transit of the companion planet HD 149026b, which occurred on 2005 June 25. These velocities provide a high-cadence observation of the Rossiter-McLaughlin effect, the shifting of photospheric line profiles that occurs when a planet occults a portion of the rotating stellar surface. We combine these radial velocities with previously published radial velocity and photometric data sets and derive a composite best-fit model for the star-planet system. This model confirms and improves previously published orbital parameters, including the remarkably small planetary radius, the planetary mass, and the orbital inclination, found to be Rp/RJup = 0.718 ± 0.065, Mp/MJup = 0.352 ± 0.025, and I = 86.1° ± 1.4°, respectively. Together the planetary mass and radius determinations imply a mean planetary density of 1.18(-0.30)(+0.38)g cm(-3). The new data also allow for the determination of the angle between the apparent stellar equator and the orbital plane, which we constrain to be λ = -12° ± 15°.