A novel cationic gemini surfactant with the hydrophenanthrene structure has been synthesized from dehydroabietic acid by use of conventional thermal conditions and microwave irradiation. Its structure was confirmed by IR, 1H NMR, and 13C NMR spectroscopy. It was found that microwave-assisted synthesis is an efficient means of preparation of this cationic gemini surfactant, with shorter reaction times and higher yields. The title compound had high surface activity. The CMC was 3.1 × 10−5 mol L−1, γ CMC was 26.3 mN m−1, and emulsifying power (with benzene) reached five days. Comparison of this gemini surfactant and its monomeric counterpart proved the gemini surfactant was more surface active.