Concrete is known as a heterogeneous product which is composed of complex chemical composition and reaction. The development of concrete thermal effect during early age is critical on its future structural health and long term durability. When cement is mixed with water, the exothermic chemical reaction generates hydration heat, which raises the temperature within the concrete. Consequently, cracking may occur if the concrete temperature rises too high or if there is a large temperature difference between the interior and the exterior of concrete structures during early age hydration. This paper describes the contribution of novel Fabry-Perot (FP) fiber optic temperature sensors to investigate the thermal effects of concrete hydration process. Concrete specimens were manufactured under various water-to-cement (w/c) ratios from 0.40 to 0.60. During the first 24 hours of concreting, two FP fiber optic temperature sensors were inserted into concrete specimens with the protection of copper tubing to monitor the surface and core temperature change. The experimental results revealed effects of w/c ratios on surface and core temperature developments during early age hydration, as well as demonstrating that FP fiber optic sensors are capable of capturing temperature variation in the concrete with reliable performance. Temperature profiles are used for calculating the apparent activation energy ($E_a$) and the heat of hydration (H(t)) of concrete, which can help us to better understand cement hydration.