The direct formation of amorphous layers on (111) Ge, GaP, and GaAs crystals is demonstrated to occur when these are transiently melted with 2.5‐ns UV laser pulses below particular radiation energy density thresholds. Above these thresholds, the melt resolidification rate is reduced and in each case the (111) crystals exhibit a transition to a regime of profuse twin defect nucleation. Also for each material, laser melting of (001) crystal leads to defect‐free recrystallization when amorphization does not occur. All amorphous layers exhibit a cellular thickness modulation which may be due to a fundamental instability in the recrystallization interface.