The invention discloses a porous carbon modified glassy carbon electrode, which is prepared by the steps of pyrolyzing sodium alginate under the protection of nitrogen, cooling a carbon material obtained by pyrolysis to room temperature, adding the carbon material into hydrochloric acid with the concentration of 1-5mol/L, soaking and stirring for 20-60 minutes, washing with distilled water to be neutral, and drying to obtain porous carbon; dispersing porous carbon into N,N-dimethylformamide, and carrying out uniform ultrasonic dispersion to obtain a porous carbon dispersion liquid; and polishing a glassy carbon electrode with Al2O3 until the mirror surface is smooth, then sequentially carrying out ultrasonic cleaning with ethanol and secondary distilled water, washing with the secondary distilled water, blow-drying, dropwise adding the porous carbon dispersion liquid, and drying to obtain the porous carbon modified glassy carbon electrode. A three-electrode system composed of the porous carbon modified glassy carbon electrode can distinguish oxidation peaks of catechol, hydroquinone and resorcinol, significantly enhances electrochemical signals of three target objects, improves thedetection sensitivity, and can be used for determination of actual environmental water samples.