Background: The colony-forming, green microalga Botryococcus braunii secretes large amounts of petroleum-like hydrocarbons, which enables non-destructive in situ extraction (milking) of these extracellular hydrocarbons during culture growth continuously without cell lysis. This study compares the suitability of 15 different solvents, including alkanes, halogens, and green solvents, for in situ extraction of B. braunii race B (Showa strain) hydrocarbons after acclimation to moderate salinity stress. Findings: After 24 h of extraction, bio-based terpene 'green' solvents such as gamma-terpinene showed the highest hydrocarbon extraction capacity, with GC peak areas of botryococcenes around 10-fold greater than with conventional alkane solvents. Brominated alkanes and liquid perfluorocarbons (FCs) formed a lower phase to algal cultures rather than an upper phase as with other solvents, but only bromodecane effectively captured extracellular hydrocarbons as is the case with conventional alkane solvents. However, bromodecane and all green solvents were too toxic for two-phase continuous culture contact hydrocarbon milking, leading to 33-100% chlorophyll content loss in algal cultures. Conclusions: To overcome the adverse effects of these promising solvents, future research should focus on their application in short-term extraction period-milking systems to minimize algal-solvent contact and enable continuous extraction.