We report the synthesis, micellar structures, and multifunctional sensory properties of new conjugated rod-coil block copolymers, poly(3-hexylthiophene)-block-poly(2-(dimethylamino)ethylmethacrylate)(P3 HT-b-PDMAEMA). The new copolymers, synthesized by atom transfer radical polymerization of P3HT macroinitiator, consisted PDMAEMA coil lengths of 43, 65, and 124 repeating units. All the P3HT-b-PDMAEMA copolymers exhibit a similar low critical solution temperature in water around 33 degrees C. The micellar structures of the synthesized polymers were characterized by AFM, TEM, and dynamic light scattering, by varying temperature, pH, and water/THF composition. The micelles of P3HT(20)-b-PDMAEMA(43) in water had a reversible size change from 75 +/- 5 nm to 132 +/- 5 nm on heating from 25 to 55 degrees C and reduced to the original size during cooling. In addition, the micellar size also showed a significant pH dependence, changing from 67 +/- 8 nm (pH = 12) to 222 +/- 6 nm (pH = 4), depending on the protonation of the PDMAEMA blocks and their electrostatic repulsion. The micellar structure of three P3HT-b-PDMAEMA copolymers changed from spheres, to vesicles, and finally to larger sphere micelles as the solvent composition varied from 0 to 100 wt % water in the mixed solvent. The different micellar structures of P3HT(20)-b-PDMAEMA(43) solution led to a red-shift on the absorption or photoluminescence spectra and exhibited the emission colors of yellow, orange, red, and dark red with increasing the water content. This study suggested that new copolymers had potential applications as multifunctional sensory materials toward temperature, pH, and solvent. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 147-155, 2011