In this study, a class of hydrophilic‐alternating‐lipophilic copolymers (HaLCs) has been designed, and the polymers were prepared and applied in the demulsification of stable water‐in‐oil (W/O) emulsions. The results showed that the efficiency of HaLCs can reach 100 % in less than 10 min even at room temperature. The optimum dosages for l‐, s‐, and t‐ (linear, square and tetrahedron‐shaped) HaLC were 125, 313, and 156 ppm, respectively. This finding is helpful in understanding the demulsification process and development of demulsifiers with higher efficiency in the future, which is important in the petroleum industry.