A crystalline modification V of emamectin benzoate, exhibiting at least 3 of the following reflexes in an X-ray powder diffractogram recorded using Cu—Kα radiation at 25° C.: 2θ=4.34±0.2  (1) 2θ=10.58±0.2  (2) 2θ=12.32±0.2  (3) 2θ=15.19±0.2  (4) 2θ=18.57±0.2  (5) 2θ=20.41±0.2  (6) A process for the preparation of emamectin benzoate in the aforementioned form comprises i) preparing a solution of a solid form of emamectin benzoate in a solvent comprising ethyl acetate and n-hexane; ii) effecting crystallization of emamectin benzoate from the solution; and iii) isolating the emamectin benzoate formed. The crystalline modification V can be formulated to any suitable pesticidal formulations.