Using specified conditions, we succeeded in observing the isotropic-nematic (Iso-N) liquid crystal phase transition at surfaces followed by that in bulk for the first time. An additional heat anomaly peak was found at a higher temperature side of a main phase transition peak using highly sensitive differential scanning calorimetry (HS-DSC). The peak is pronounced particularly in the cooling process, since the transition starts at surfaces on cooling. The temperature dependence of retardation allows us to safely conclude that the higher temperature peak that appeared in HS-DSC is attributed to the Iso-N transition at surfaces. These measurements also indicate that the surface transition is of first order. These behaviors were theoretically explained by generalized Maier-Saupe theory.