ZnO flower-like (ZFL) and needle (ZLN) structures were synthesized and embedded into UV-curable acrylic resin (EB), with the aim to study the effect of filler loading on the piezoelectric properties of the resulting composite films. The composites showed uniform dispersion of fillers within the polymer matrix. However, by increasing the filler amount, the number of aggregates increased, and ZnO fillers appeared not to be perfectly embedded in polymer film, indicating poor interaction with acrylic resin. The filler content increase caused an increase in glass transition temperature (Tg) and a decrease in storage modulus in the glassy state. In particular, compared with pure UV-cured EB (Tg = 50 °C), 10 wt.% ZFL and ZLN presented Tg values of 68 and 77 °C, respectively. The piezoelectric response generated by the polymer composites was good when measured at 19 Hz as a function of the acceleration; the RMS output voltages achieved at 5 g were 4.94 and 1.85 mV for the composite films containing ZFL and ZLN, respectively, at their maximum loading levels (i.e., 20 wt.%). Further, the RMS output voltage increase was not proportional to the filler loading; this finding was attributable to the decrease in the storage modulus of the composites at high ZnO loading rather than the dispersion of filler or the number of particles on the surface.