The effects of small neutral molecules on the liquid-crystalline ordering of dimyristoyl-phosphatidylcholine (DMPC)/dihexanoyl-phosphatidylcholine (DHPC) bicelles (q = 3.0 and 3.5) were studied via H-2, P-31, and C-13 variable-temperature NMR. The addition of chloroform (up to similar to90 mM, with a lipid concentration of similar to120 mM) was observed to reduce the temperature onset of bicelle ordering by up to similar to10 degreesC, likely resulting from the depression of the DMPC phase transition temperature. The temperature for the collapse of the bicelle phase was also significantly reduced; the observed effects amount to a downward shift in temperature (and reduction in range) of the liquid-crystalline portion of the bicelle phase diagram with increasing dopant concentration. Other model dopants (e.g., tetrahydrofuran and benzene) yielded smaller effects. Additionally, the variable bicelle alignment permitted the characterization of the ordering of chloroform molecules within the lipid phase.