The author has been engaged in the development of a novel optical fiber probe using scanning near-field optical microscope (SNOM) with an efficient, plasmonic and asymmetric Metal-Insulator-Metal (MIM) structure at the probe tip. As a metallic layer, titanium nitride (TiN), one of the alternative plasmonic materials, is selected. A pulsed laser deposition (PLD) is used to fabricate the film by high-power Nd:YAG laser. The PLDed films have been analyzed by X-ray diffractometer (XRD), UV-Vis/NIR spectrophotometer, scanning electron microscope (SEM), and X-ray photoelectron spectroscopy (XPS). Though most of previous PLD studies of TiN film used a titanium target with reactive gases, the study presented in this chapter has significant features of (1) a hot pressed target of crystalline TiN powder and (2) third harmonic of injection-seeded Nd:YAG laser which have temporally smoothed Gaussian with a constant pulse energy. The very first PLD process has succeeded to fabricate flat and dense films of a few hundred nanometers. The TiN film, which lustered like gold, indicated two peaks at 36.7° (111) and 42.6° (200) in XRD patterns that correspond to crystal structure of TiN. An elementary analysis of the TiN film has carried out using XPS, and appropriate spectra with chemical shifts were observed.Keywords: alternative plasmonic material, titanium nitride (TiN), plasmonic thin film, pulsed laser deposition (PLD), crystalline thin film, third harmonic of pulsed Nd:YAG laser, X-ray diffractometer (XRD), electromagnetic FEM simulation, X-ray photoelectron spectroscopy (XPS)