A polyvinylidenefluoride (PVDF) having high mechanical properties both at room temperature and at high temperatures, having very good processability and high thermochemical resistance to dehydrofluorination, is prepared by means of a polymerization process of vinylidenefluoride in aqueous emulsion at a temperature comprised between 95.degree. and 120.degree. C., in the presence of a chain transfer agent. In this way it is possible to obtain, using non-hazardous peroxidic initiators (for instance diterbutylperoxide), a PVDF particularly suitable for applications where high mechanical and thermochemical resistance properties are required, such as for instance the manufacture of articles for chemical industry (pipes, valves, fittings, tanks, heat exchangers, membranes, flanges, etc.).