Alginate like extracellular polymers (ALE) recovered from flocculent sludge has been identified as a kind of highly valuable biomaterials. However, the extraction protocols limit the production of biopolymers as ALE extracted from flocculent sludge is at a lower level, around 90–190 mg/g VSS. Under this circumstance, the eco-friendly and effective optimizations for the ALE extraction protocols are expected, and thus surfactants have gained an attention to enhancing the ALE extraction. With this study, different surfactants with different structures and chemical characteristics, such as sodium dodecyl sulfate (SDS), cetyltrimethylammonium bromide (CTAB) and octyl phenyl polyoxyethylene ether (Triton X-100), were experimented to improve the ALE extraction, and in turn the optimal conditions and the associated mechanisms were evaluated and figured out. The experimental results indicated that surfactants could enhance the ALE extraction but also improve the alginate purification of ALE. With the optimal dosage of surfactants, the ALE extraction increased from 124.1 mg/g VSS to about 222.8–281.9 mg/g VSS, and the alginate purify was at around 54%–70%, in which the efficiency of the ALE extraction was improved by 79.5%–127.2%. Among others, Triton X-100 had the best performance on improving the ALE extraction, followed by CTAB and SDS. The mechanisms of surfactants on enhancing the ALE extraction and improving the alginate purify can be attributed to: i) surfactants micelles, which can solubilize flocs and extracellular biopolymers; ii) similar structures of surfactants and ALE, which follows the rule of “like dissolves like”; iii) functional groups adsorption, which facilitates the ALE release from matrixes. In a word, the optimized extraction protocol by using surfactants can be effectively applied to extract ALE from flocculent sludge.