To improve the carbon to nitrogen (C/N) ratio of harvested microalgae biomass for better producing biogas by fermentation, biodegradable cationic starch with high C/N ratio were synthesized to harvest Chlorella vulgaris. The impact of pH was also studied as the zeta potential of both microalgae and cationic starch would change with pH. Results indicated the cationic starch can harvest above 99% of the microalgae and the C/N ratio can rise from 7.50 to 7.90. The zeta potential of microalgae always kept negative and presented a trend of descending firstly and then upgrade. The maximum microalgae biomass flocculation capacity of 1 g cationic starch was 8.62 g with the help of self-flocculation at pH 3. The concentration of flocs formed at pH 11 was 25.74 g L-1 and the diameter was 0.553mm which was much larger than the flocs formed at pH 3 (0.208 mm).