Lead-free piezoelectric ceramics (Bi0.5Na0.5)0.94(Ba1-xSrx)0.06TiO3 (abbreviated as BNBST-100x, with x ranges from 0.02 to 0.1) have been investigated. Effects of amount of Sr-substitution on the electrical properties and crystal structure of the ceramics were studied. The BNBST-100x ceramics sintered at 1200°C for 2h in air have high density around 5.69~5.75g/cm3. X-ray diffraction (XRD) analysis shows that all of the BNBST-100x ceramics have pure perovskite structure. At high amount level of Sr-substitution, the crystal structure of the samples changes from rhombohedral to tetragonal symmetry. Piezoelectric and dielectric measurements reveal that Sr-substitution amount within a certain range will lead to the increase of piezoelectric coefficient (d33), electromechanical coupling factor (kp), and relative dielectric constant (ε33 T/ε0). At 6 mol% Sr-substitution level, the d33 and kp of the ceramics reach maximum, with values of 168 pC/N and 34%, respectively.