We characterize the Brillouin gain spectra (BGS) in perfluorinated graded-index polymer optical fibers (PFGI-POFs) with 62.5-μm core diameter. First, we show that the Stokes power is extremely high compared to that of a standard PFGI-POF with 120-μm core, and discuss the Brillouin threshold power. Then, we demonstrate that the PFGI-POF length has little influence on the BGS when the length is longer than 50 m. We also predict that, at 1.55-μm wavelength, it is difficult to reduce the Brillouin threshold power of PFGI-POFs below that of long silica single-mode fibers even if their core diameter is sufficiently reduced to satisfy the single-mode condition. Finally, we confirm the Brillouin linewidth narrowing effect.