Coupling of charge and spin degrees of freedom is a critical feature of correlated electron oxides, as represented by the spin-related mechanism of a Cooper pair under high-T c superconductivity. A doublon-holon pair generated on an antiferromagnetic spin background is also predicted to attract each other via the spin-spin interaction J, similar to a Cooper pair, while its evidence is difficult to obtain experimentally. Here, we investigate such an excitonic effect by electroreflectance spectroscopy using terahertz electric field pulses in undoped cuprates: Nd2CuO4, Sr2CuO2Cl2, and La2CuO4. Analyses of the spectral changes of reflectivity under electric fields reveal that the splitting of odd-parity and even-parity excitons, a measure of doublon-holon binding energy, increases with J. This trend is reproduced by t-J-type model calculations, providing strong evidence of the spin-related doublon-holon pairing. Agreement with the calculations supports the s-wave symmetry of the doublon-holon pair in contrast to the d-wave Cooper pair in doped cuprates.