Thin ferroelectric films of lead zirconate titanate (PbZr1-xTixO3 or PZT) are basic components for MEMS systems [1]. Extreme electromechanical properties of PZT as well known [2] are observed in narrow band of PZT solid solutions with a composition corresponding to morphotropic phase boundary (MPB) (at х≈0.46-0.48), that divides tetragonal and rhombohedral ferroelectric phases. In [3] it is assumed that such properties are linked to the ferroelectric phase monoclinic modification in the area of MPB, which stability depends on element heterogeneity, microstructure and mechanical tensions. The search for compositions with most suitable electromechanical parameters involves accurate composition variation (Zr and Ti proportion) within the region of MPB.  The films were formed by two-stage ex-situ method. Firstly, amorphous films were deposited onto platinized silicon substrate by the RF magnetron sputtering of a ceramic target. To crystallize the perovskite phase, they were annealed at 580°C. To vary the composition of the films, the change in the distance from the target to the substrate (d) in the range 30-70 mm with the step 10 mm was applied. The relationship between the SHG-signal, composition and microstructure of the films was investigated. The phase state, composition and microstructure of the films was determined using SEM Tescan Vega II LMU and Zeiss EVO-40. To study the SHG signal, we used femtosecond laser (Ti: sapphire, Avesta-Project, Russia) with a wavelength of 800 nm.  The SEM data have shown the change of PZT composition (elemental ratio of Zr/Ti) within 2% in the area of MPB. The microstructure of the films was a set of polycrystalline spherulite blocks with a radiant structure (Fig. 1,a). With increasing target-substrate distance the density and shape of the segments changed significantly. The magnitude of SHG signal strongly changed, with the maximum corresponding to the films deposited at d = 50 mm (Fig. 1,b), too. In the work the relationship the between PZT composition, SHG signal and microstructure of the films is discussed.