(1-x)(Na0.50K0.45Li0.05)NbO3-(x)Ca(Zr0.50Ti0.50)O3 (NKLN-CZT, x = 0-0.08) powders were synthesized by the malic acid complex solution method, and NKLN-CZT solid solutions were then fabricated using a conventional solid-state reaction technique. The piezoelectric properties of the resulting materials were measured, and the x = 0.02 sample was found to exhibit the maximum longitudinal-length-mode piezoelectric coefficient and radial-mode electromechanical coupling factor values of 238 pC/N and 35%, respectively. On the basis of both the results for piezoelectric properties and for the local structural analysis using high-energy X-ray diffraction (HEXRD), measuring the degree of distortion of NbO6 octahedra using HEXRD can be an effective method for the development of high-performance piezoelectric materials.