Crystalline form V of agomelatine (I) is new. Crystalline form V of agomelatine ((I); N-[2-(7-methoxy-1-naphthyl)ethyl]acetamide) having powder X-ray diffraction diagram, measured using a diffractometer (copper anticathode) and expressed in terms of inter-planar distance d (8.979-3.239 A[deg]), Bragg's angle 2 theta (9.84-27.51 degrees), intensity and relative intensity (15-100 percentage with respect to the most intense), is new. Independent claims are included for: (1) the preparation of (I); and (2) a composition comprising (I) and, inert and non-toxic carriers. ACTIVITY : Hypnotic; Tranquilizer; Antidepressant; Cardiovascular-Gen.; Sedative; Muscular-Gen.; Immunomodulator; Neuroleptic; Anorectic; Anticonvulsant; Antidiabetic; Antiparkinsonian; Nootropic; Antimigraine; Neuroprotective; Endocrine-Gen.; Contraceptive; Cytostatic. MECHANISM OF ACTION : Melatoninergic receptor agonist.