The demulsification effect of three types of block copolymers, BP123, BPF123, and H123, with the same PEO and PPO segments but different hydrophobic modification groups on crude oil emulsions and the properties of oil–water interfaces were investigated using demulsification experiments, an interfacial tensiometer, and surface viscoelastic and zeta potential instruments in this paper. The results showed that the hydrophobic modification group of the block copolymers had great effects on the demulsification performance. The H123 block copolymers with the strongest hydrophobicity had the best demulsification effect on the crude oil emulsions. The properties of the oil–water interfaces indicated that the modified block copolymers achieved the demulsification of crude oil emulsions by reducing the strength of the oil–water interfacial film and the interfacial tension.