Doping control has been a key challenge for electronic applications of van der Waals materials.Here,we demonstrate complementary doping of black phosphorus using controlled ionic intercalation to achieve monolithic building elements.We characterize the anisotropic electrical transport as a function of ion concentrations and report a widely tunable resistivity up to three orders of magnitude with characteristic concentration dependence corresponding to phase transitions during intercalation.As a further step,we develop both p-type and n-type field effect transistors as well as electrical diodes with high device stability and performance.In addition,enhanced charge mobility from 380 to 820 cm2/(V·s) with the intercalation process is observed and explained as the suppressed neutral impurity scattering based on our ab initio calculations.Our study provides a unique approach to atomically control the electrical properties of van der Waals materials,and may open up new opportunities in developing advanced electronics and physics platforms.