Helium purification has become more important for increasing demands in scientific and industrial applications. In this work, we demonstrated that the porous silicene can be used as an effective ultimate membrane for helium purification on the basis of first-principles calculations. Prinstine silicene monolayer is impermeable to helium gas with a high penetration energy barrier (1.66 eV). However, porous silicene with either Stone-Wales (SW) or divacancy (555,777 or 585) defect presents a surmountable barrier for helium (0.33 to 0.78 eV) but formidable for Ne, Ar, and other gas molecules. In particular, the porous silicene with divacancy defects shows high selectivity for He/Ne and He/Ar, superior to graphene, polyphenylene, and traditional membranes.