We report switching behavior between the ferroelectric β phase and the paraelectric α phase in polyvinylidene fluoride–multiwalled carbon nanotube (PVDF–CNT) nanocomposite. The PVDF–CNT nanocomposite thin films are prepared on Au/Si substrates using spin coating technique. Various characterization techniques reveal the interaction of PVDF with CNTs as a nucleating agent for nucleating ferroelectric β phase in PVDF. A wavelength-independent reversible phase transformation behavior is observed for the PVDF–CNT nanocomposite during the measurement of laser power modulated micro-Raman spectroscopy (533 and 632 nm lasers). This observation opens up an innovative route where we can control the interactions between polar nanocarbons and PVDF using visible light.