In order to study the effect of cleaning operations on polyvinylidene fluoride (PVDF) hollow fiber membrane stability, ageing of two PVDF based membranes (one is additive free, the other contains hydrophilic additives) in contact with sodium hypochlorite solutions with various pH values has been studied. The aim of this experimental study was to identify the degradation mechanisms and to gain a better understanding of the effect of the (macro)molecular structure changes on the mechanical and functional properties of the membranes. In both membranes, double bond formation, chain scission and crosslinking are observed and all these processes (except crosslinking) are faster in acidified solutions than in natural NaOCl solutions (pH 11.5). It can be deduced that if ionic processes such as dehydrofluorination occur, radical processes resulting from the presence of hypochlorous acid and perhaps its coexistence with the ClO− ion, predominate in acidified solutions. The presence of non-fluorinated aliphatic or cycloaliphatic additives, which are highly reactive with bleach, accelerates chain scission at the expense of crosslinking. In the chosen conditions (135 days in 4000 ppm bleach solutions at 40 °C), PVDF chains are degraded but not enough to induce polymer embrittlement. While in the additive free membrane no significant change of the use properties has been observed, the polymeric additives of the other membrane are completely destroyed, leading to a decrease of the membrane hydrophilicity, but their destruction improves the membrane selectivity by a decrease of the average porosity.