The principal values of the C-13 chemical-shift tensor (CST) for biphenyl have been determined with the FIREMAT experiment. The internal dihedral angle between the benzene rings in biphenyl is estimated to fall between 10 and 20 degrees on the basis of quantum mechanical calculations of the CST principal values. A composite model of motion in the system, with contributions both from internal jumping between enantiomeric structures and from overall molecular librations, yields the smallest variance between predicted and measured values for an internal twist angle of 15 degrees between the rings and a mean libration angle of +/- 12 degrees from the most favored molecular orientation. The composite model is clearly preferred to a motionless model (with > 98% probability) and is also preferred over either of the isolated contributing dynamics, i.e., only libration or only internal jumping.