Efficient pigment extraction is a key factor influencing the economic feasibility of microalgal biorefineries. Ethanol, acetone, ethyl acetate, and hexane were evaluated for the batch extraction of chlorophyll a, chlorophyll b, and carotenoids from Chlorella sorokiniana and Heterochlorella luteoviridis. Solvent‐to‐biomass ratios did not affect extraction results in most cases. Ethanol showed the highest efficiency in the recovery of chlorophylls, presenting high extraction yields. Acetone was among the most efficient solvents to extract violaxanthin, lutein, zeaxanthin, and carotene from both microalgae, proving to be generally suitable to this application. Conductor‐like screening model for real solvent segment activity (COSMO‐SAC) corroborated experimental results, proving to be an important tool in the screening of solvents for extraction processes.