We report unique thermo-optical characteristics of DNA-Cetyl tri-methyl ammonium (DNA-CTMA) thin solid film with a large negative thermo-optical coefficient of -3.4×10-4/°C in the temperature range from 20°C to 70°C without any observable thermal hysteresis. By combining this thermo-optic DNA film and fiber optic multimode interference (MMI) device, we experimentally demonstrated a highly sensitive compact temperature sensor with a large spectral shift of 0.15 nm/°C. The fiber optic MMI device was a concatenated structure with single-mode fiber (SMF)-coreless silica fiber (CSF)-single mode fiber (SMF) and the DNA-CTMA film was deposited on the CSF. The spectral shifts of the device in experiments were compared with the beam propagation method, which showed a good agreement.