In this paper, we discuss an impact of thin titanium dioxide (TiO(2)) coatings on refractive index (RI) sensitivity and biofunctionalization of long-period gratings (LPGs). The TiO(2) overlays on the LPG surfaces have been obtained using atomic layer deposition (ALD) method. This method allows for a deposition of conformal, thickness-controlled, with well-defined optical properties, and high-RI thin films which are highly desired for optical fiber sensors. It has been found that for LPGs working at a dispersion turning point of higher order cladding modes only tens of nanometers of TiO(2) overlay thickness allow to obtain cladding mode transition effect, and thus significant improvement of RI sensitivity. When the TiO(2) overlay thickness reaches 70 nm, it is possible to obtain RI sensitivity exceeding 6200 nm/RIU in RI range where label-free sensors operate. Moreover, LPGs with TiO(2)-enhanced RI sensitivity have shown improved sensitivity to bacteria endotoxin (E. coli B lipopolysaccharide) detection, when TiO(2) surface is functionalized with endotoxin binding protein (adhesin) of T4 bacteriophage.