The Lunar Laser Ranging experiment has been active since 1969 when Apollo astronauts placed the first retroreflector on the Moon. The data accuracy of a few centimeters over recent decades, joined to a new numerically integrated ephemeris, DE421, encourages a new analysis of the lunar physical librations of that ephemeris, and especially the detection of three modes of free physical librations (longitude, latitude, and wobble modes). This analysis was performed by iterating a frequency analysis and linear least-squares fit of the wide spectrum of DE421 lunar physical librations. From this analysis we identified and estimated about 130–140 terms in the angular series of latitude librations and polar coordinates, and 89 terms in the longitude angle. In this determination, we found the non-negligible amplitudes of the three modes of free physical libration. The determined amplitudes reach 1.296′′ in longitude (after correction of two close forcing terms), 0.032′′ in latitude and 8.183′′ × 3.306′′ for the wobble, with the respective periods of 1056.13 days, 8822.88 days (referred to the moving node), and 27257.27 days. The presence of such terms despite damping suggests the existence of some source of stimulation acting in geologically recent times.