Manifestations of quantum interference effects in macroscopic objects are rare. Weak localization is one of the few examples of such effects showing up in the electron transport through solid state. Here, we show that weak localization becomes prominent also in optical spectroscopy via detection of the electron spin dynamics. In particular, we find that weak localization controls the free electron spin relaxation in semiconductors at low temperatures and weak magnetic fields by slowing it down by almost a factor of two in n-doped GaAs in the metallic phase. The weak localization effect on the spin relaxation is suppressed by moderate magnetic fields of approximately 1 T, which destroy the interference of electron trajectories, and by increasing the temperature. The weak localization suppression causes an anomalous decrease of the longitudinal electron spin relaxation time T1 with magnetic field, in stark contrast with the well-known magnetic-field-induced increase in T1. This is consistent with transport measurements, which show the same variation of resistivity with magnetic field. Our discovery opens up a vast playground to explore quantum magnetotransport effects optically in the spin dynamics.