Compounds and solid solutions of bismuth ferrite (BiFeO₃)—barium titanate (BaTiO₃) system are of great scientific and engineering interest as multiferroic and potential high-temperature lead-free piezoelectric materials. In the present paper, the results of research on the synthesis and characterisation of 0.67Bi₁.₀₂FeO₃–0.33BaTiO₃ (67BFBT) ceramics in terms of crystal structure and dielectric and piezoelectric properties are reported. It was found that the produced 67BFBT ceramics were characterised by a tetragonal crystal structure described by the P4mm space group, an average crystallite size <D> ≈ 80 nm, and an average strain <ε> = 0.01%. Broad-band dielectric spectroscopy (BBDS) was employed to characterise the dielectric response of polycrystalline ceramics. The frequency range from ν = 10⁻¹ Hz to ν = 10⁵ Hz was used to characterise the influence of the electric field strength on dielectric response of the ceramic sample at room temperature. The dielectric spectra were checked for consistency with the Kramers–Kronig test, and the high quality of the measurements were confirmed. The electric equivalent circuit method was used to fit the dielectric spectra within the frequency range that corresponded to the occurrence of the resonant spectra of the radial mode for thin disk sample, i.e., from ν = 10⁵ Hz to ν = 10⁷ Hz and the temperature range from T = −20 °C to T = 50 °C. The electric equivalent circuit [R_sCPE₁([L₁R₁C₁]C₀)] was used, and good fitting quality was reached. The relevant calculations were performed, and it was found that the piezoelectric charge coefficient exhibited a value of d₃₁ = 35 pC/N and the planar coupling factor was k_p = 31% at room temperature. Analysis of impedance spectra performed in terms of circumferential magnetic field made it possible to establish an influence of magnetic field on piezoelectric parameters of 67BFBT multiferroic ceramics. Additionally, the “magnetic” tunability of the modulus of the complex dielectric permittivity makes 67BFBT a sensing material with vast potential.