The interaction of sodium cholate (NaC) with (6,5) single-wall carbon nanotubes (SWNTs) is investigated using photoluminescence spectroscopy. Dilution of SWNT-NaC suspensions is accompanied by changes in the exciton PL quantum yield and peak emission energy. An abrupt change of the exciton emission peak energy at NaC concentrations between 10 and 14 mM indicates strongly cooperative formation of a micellar phase on (6,5) SWNT surfaces with a Hill coefficient of n(H) = 65 +/- 6. This is in contrast to the formation of free NaC micelles with aggregation numbers of only about 4 and suggests that the cooperativity of NaC micelle formation on nanotube surfaces is strongly substrate-enhanced. The temperature dependence of this previously unobserved transition is used for a determination of Delta(mic)(G) over bar (Theta)/(1 + beta) = -(11.4 +/- 0.2) kJ.mol(-1) which, for typical Na+ counterion binding with beta approximate to 0.2, yields a free SWNT-NaC micellization enthalpy Delta(mic)(G) over bar (Theta) of -13.7 kJ.mol(-1).