Five new polar steroids, polyhydroxysterols 2-5 and the glycoside leviusculoside J (7), were isolated, along with the previously known compounds 1, 6, 8, and 9, from the alcoholic extract of the Far Eastern starfish Henricia leviuscula. The structures of novel compounds were elucidated by interpretation of spectral data (mainly 2D-NMR), and the stereochemistry of chiral centers in the side chain of sterols 2 and 3 was determined by using J-based configuration analysis and the modified Mosher's method. Steroids 1, 3, 6, 7, and 9 showed moderate hemolytic activity in the mouse erythrocytes assay.