Unrevealing local magnetic and electronic correlations in the vicinity of charge carriers is crucial in order to understand rich physical properties in correlated electron systems. Here, using high-energy optical conductivity (up to 35 eV) as a function of temperature and polarization, we observe a surprisingly strong spin polarization of the local spin singlet with enhanced ferromagnetic correlations between Cu spins near the doped holes in lightly hole-doped La1.95Sr0.05Cu0.95Zn0.05O4. The changes of the local spin polarization manifest strongly in the temperature-dependent optical conductivity at similar to 7.2 eV, with an anomaly at the magnetic stripe phase (similar to 25 K), accompanied by anomalous spectral-weight transfer in a broad energy range. Supported by theoretical calculations, we also assign high-energy optical transitions and their corresponding temperature dependence, particularly at similar to 2.5, similar to 8.7, similar to 9.7, similar to 11.3, and similar to 21.8 eV. Our result shows the importance of a strong mixture of spin singlet and triplet states in hole-doped cuprates and demonstrates a new strategy to probe local magnetic correlations using high-energy optical conductivity in correlated electron systems.