Highly sensitized NIR emission was modulated using an ESIPT ligand in a Nd-complex, to achieve a substantially elongated NIR lifetime in cyclohexane suspension with a value of 16.89 μs at RT, and anomalous themally-activated NIR emission with the temperature increasing from 77 to 300 K for the first time, which was further designed into a remote and in situ optical fiber sensing device.