In this paper, we first describe the electrochemical behavior Of C-60 and Of C-70 embedded in films of lipids and cationic amphiphiles on basal-plane pyrolytic graphite (BPG) electrodes in aqueous media. The electrode modifiers used were mainly tridodecylmethylammonium bromide (3C(12)N(+)Br(-)), tetraalkylammonium bromide (4C(n)N(+)Br(-), n = 5, 6, 7, 8, 10, 12, and 16), and dihexadecyldimethylammonium poly(styrene sulfonate) (2C(16)N(+)PSS(-)). The generated radical monoanions and dianions of C-60 and C-70 on the electrodes were stable during continuous potential cycling, but the C-70 radical monoanion became unstable after the generation of C-70(.3-), which is not consistent with the behavior Of C-60. On the basis of the electrolyte dependence, a possible electron-transfer mechanism of fullerenes/lipid (amphiphile) -coated electrodes was presented. Second, a spectroelectrochemical study was conducted for C-60/3C(12)N(+)Br(-)-modified electrodes, and the results of simultaneous measurements Of Current and absorbance changes during potential cycling gave direct evidence of the generation Of C-60(.-) in aqueous systems. Third, the strong phase-transition-dependent electrochemistry of fullerenes in the films on electrodes was demonstrated in which 2C(16)N(+)PSS(-) and 4C(n)N(+)Br(-) (n = 10, 12, 16) were used as the lipid and amphiphile matrices, respectively. Finally, chemical generation of fullerene radical anions C-60(.-) and C-70(.-) using Na2S2O4 as a reducing reagent at lipid thin films containing C-60 or C-70 was investigated. Visible-near-IR spectra revealed that C-60(.-) and C-70(.-) were chemically produced in cationic lipid films in aqueous media. All results obtained suggest that the charge of the lipid matrix and the hydrophobic microenvironments in the lipid films play an important role in the generation of anions of C-60 and C-70 in these film states in aqueous media.