A 0–3 piezoelectric ceramic-Portland cement (PC) composite with different compositions was fabricated and investigated with the following components: BZT (40, 50, and 60 vol% represented as BZT40, BZT60, and BZT60, respectively) and epoxy resin (0, 3, 5, and 7 vol% represented as ER0, ER3, ER5, and ER7, respectively). Experimental results show that increasing ER content (0–7 vol%) led to an increase in density (ρc), for 50% BZT increased from 3.42 to 3.55 g/cm3 and a decrease in porosity, from 12.71 to 11.67% (for 50%BZT) and acoustic impedance (Zc) value increased from 9.67 to 8.84 × 106 kg/m·s2. Both εr and tanδ decreased with increasing ER content. ER as the third phase resulted in a lower leakage current and the BZT60ER7 composite is found to have the lowest leakage current (20 μA). Increasing ER content led to a decrease in the piezoelectric charge coefficient (d33). However, a notable increase in piezoelectric voltage coefficient (g33) with increasing ER content up to 3 vol% was found. The optimization of both Zc and g33 in this study can be observed in BZT50ER3 composite (Zc = 9.16 × 106 kg/m2·s and g33 = 13.9 × 10−3 V m/N). In addition, the highest planar electromechanical coupling factor (kp = 17.97%) and thickness electromechanical coupling factor (kt = 17.75%) can be observed in BZT60ER7 composite.