KTiOPO(4) (KTP) nanocrystals have been synthesized by the modified Pechini method using ethylenediaminetetraacetic acid (EDTA) and ethylene glycol (EG) as chelating and sterification agents, respectively. Orthorhombic KTP has been obtained by calcination at 1073 K for several hours. Differential thermal and thermogravimetric (DTA-TG) analyses have been used to study the optimized heat treatment used on the precursor powder to obtain KTP nanocrystals. X-ray powder diffraction (XRD) studies on the thermally treated precursor powders indicated that nanocrystals began to crystallize at 923 K. Nanocrystals with a size dispersion distribution that fit to a lognormal function centered at 25 nm were observed by electronic microscopy. KTP nanocomposites were prepared by embedding nanocrystals in poly(methyl methacrylate) (PMMA). The photoinduced second-order susceptibility parameter and the piezo-optical coefficient were measured for the KTP nanocomposites. The optimal conditions for the generation of the frequency-doubled second harmonic generation were recorded at 391 K, and at a fundamental laser wavelength of 1064 nm and under additional treatment by polarized UV light, provided the maximum value obtained of 3.23 pm V(-1). The piezo-optical coefficients were recorded at room temperature under photoinduced treatment by a UV laser beam; the maximum value achieved was 0.673 x 10(-14) m(2) N(-1) at a pump-probe delaying time of 160 s.