The linear and nonlinear optical properties of TbCa4O(BO3)3 (abbreviated as TbCOB) single crystals were investigated for the first time. The refractive indices of TbCOB at several wavelengths were measured by using the minimum deviation method and the parameters of Sellmeier's dispersion equation were determined from the experimental data. The complete set of six second-order nonlinear optical (NLO) coefficients of TbCOB single crystals were obtained using the Maker fringe (FM) technique, with the largest d32 being on the order of 1.65 pm/V. Moreover, the phase-matching (PM) configurations of second-order harmonic generation (SHG) in the principal planes were calculated, and the largest effective NLO coefficient is deff = 0.86 pm/V along (22.56°, 180°) PM direction. The SHG conversion efficiency from 1064 nm to 532 nm of 8 mm long crystal samples without AR coating along this direction was achieved 57.1% at 28.2 mW input power, and it has a small walk-off angle of 13.8 mrad. In addition, the comparison and discussion with GdCOB and YCOB were carried out.