Poly(N-isopropylacrylamide) (PNIPAM) is an organic environment-sensitive material, which can be combined with photocatalysts to control the photocatalytic process. Herein, rodlike environment-sensitive Bi2O3 (PNIPAM/Bi2O3) was prepared by a novel one-step continuous microwave method. This new method is efficient and convenient. The as-prepared PNIPAM/Bi2O3 was very sensitive to temperature and pH, and the degradation rate in the environment of 25 degrees C and pH = 9 was 3.87 times than that in the environment of 45 degrees C and pH = 5. While Bi2O3 is under the above various environmental conditions, its degradation rate did not change obviously. More interestingly, the introduction of PNIPAM and one-step continuous microwave method was beneficial to the transformation of Bi2O3 from no specific shape to rodlike morphology without changing its crystal structure. This work not only developed a new one-step continuous microwave synthesis method, but also opened up new ideas for the controllability requirements of materials in special environment.