Bi
0.5(Na
0.68K
0.22Li
0.10)
0.5Ti
1–xCo
xO
3 lead-free perovskite ceramics (BNKLT
–xCo,
x = 0, 0.005, 0.010, 0.015 and 0.020) were fabricated via the solid-state combustion technique. A small-amount of Co
2+ ion substitution into Ti-sites led to modification of the phase formation, microstructure, electrical and magnetic properties of BNKLT ceramics. Coexisting rhombohedral and tetragonal phases were observed in all samples using the X-ray diffraction (XRD) technique. The Rietveld refinement revealed that the rhombohedral phase increased from 39% to 88% when
x increased from 0 to 0.020. The average grain size increased when
x increased. With increasing
x, more oxygen vacancies were generated, leading to asymmetry in the bipolar strain (
S–
E) hysteresis loops. For the composition of
x = 0.010, a high dielectric constant (
εm) of 5384 and a large strain (
Smax) of 0.23% with the normalized strain
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of 460 pm·V
–1 were achieved. The BNKLT–0Co ceramic showed diamagnetic behavior but all of the BNKLT
–xCo ceramics exhibited paramagnetic behavior, measured at 50 K.