In this study, a new temperature sensor with high sensitivity was achieved by four-layer Ge and B co-doped long-period fiber grating (LPFG) based on the mode coupling principle. By analyzing the mode conversion, the influence of the surrounding refractive index (SRI), the thickness and the refractive index of the film on the sensitivity of the sensor is studied. When 10 nm-thick titanium dioxide (TiO2) film is coated on the surface of the bare LPFG, the refractive index sensitivity of the sensor can be initially improved. Packaging PC452 UV-curable adhesive with a high-thermoluminescence coefficient for temperature sensitization can realize high-sensitivity temperature sensing and meet the requirements of ocean temperature detection. Finally, the effects of salt and protein attachment on the sensitivity are analyzed, which provides a reference for the subsequent application. The sensitivity of 3.8 nm/°C in the range of 5–30 °C was achieved for this new sensor, and the resolution is about 0.00026 °C, which is over 20 times higher than ordinary temperature sensors. This new sensor meets the accuracy and range of general ocean temperature measurements and could be used in various marine monitoring and environmental protection applications.