We report shear bands as a precursor structure of deformation twinning in Pb3(PO4)2. Atomic force microscopy shows “slip-line” like traces on the surface of untwinned regions of the sample. The traces are shear bands oriented along twin boundaries of the ferroelastic R3¯m-C2/c transition. Computer simulations reproduce the shear band patterns and show that each shear band is a precursor embryo of a twin wall that forms under higher shear stress. This observation reveals the structural origin of twin boundaries under stress conditions just before ferroelastic switching occurs.