Conjugated block copolymers with tunable properties have attract considerable research interests in recent years. Herein, we report a series of novel block copolymers containing conjugated poly(3-hexylthiophene) (P3HT) and poly(triethyl glycol allene) (PTA) segments which were synthesized in one pot using nickel complex as a single catalyst via distinct polymerization mechanisms. Interestingly, the P3HT-b-PTA diblock copolymers exhibit excellent thermoresponsive properties in water, and the lower critical solution temperature (LCST) is dependent on polymer concentration and the block ratio. Moreover, the diblock copolymers showed pH-responsive properties in CHCl3 with the emission color shuttled between orange and deep green upon the alternate additions of trifluoroacetic acid and triethylamine. Both P3HT-b-PTA and P3HT-b-PTA-b-P3HT block copolymers exhibit solvatochromism properties. The emission of the block copolymers can be facilely tuned through variation on solvents with the emission color spanned widely from red to blue. Very interestingly, white-light emission can be readily achieved from the P3HT-b-PTA-b-P3HT triblock copolymer in the mixture of THF and methanol with 1/3 volume ratio.