The unicellular green microalga Haematococcus pluvialis accumulates large amounts of the red ketocarotenoid astaxanthin under stress conditions such as nitrogen deficiency. In this study, we discovered an astaxanthin accumulation in H. pluvialis cells by the addition of a synthetic cationic polymer, polyethyleneimine (PEI), into the cell culture. With an increase in PEI amount, amount of astaxanthin accumulation was increased. To investigate the mechanism for the accumulation of astaxanthin by the addition of PEI in H. pluvialis cells, we measured a localization of PEI in the cells and a production of reactive oxygen species. PEI was internalized in the cells through the negatively-charged cell walls, leading to excessive production of reactive oxygen species in the cells. Thus, the increased oxidative stress by cellular uptake of PEI resulted in the acceleration of astaxanthin accumulation in H. pluvialis. (C) 2019, The Society for Biotechnology, Japan. All rights reserved.