Sunlight is an important factor in plant growth. In this regard, both blue and red lights provide significant contributions. Blue–red light dual-emission phosphors, which can be achieved by regulating energy transfer between two independent luminous centers, have recently been investigated extensively. In this study, Bi3+ and Eu3+ co-doped Na4CaSi3O9 (NCSO: Bi3+, Eu3+) phosphors are successfully synthesized via a high-temperature solid-phase method at approximately 900 °C for a few hours. X-ray powder diffraction is used to verify the crystal structure, phase purity, and structural refinement of the NCSO-based phosphors. Upon light excitation at 299 nm, the phosphors show blue–red dual emission. The blue emission (300–500 nm) may have originated from the 3P1 → 1S0 transition of Bi3+, whereas the red emission (575–725 nm) is attributable to the 5D0 → 7FJ (J = 1, 2, 3 and 4) transition of Eu3+ ions. Energy transfer from Bi3+ to Eu3+ is systematically investigated and the thermal stability of the phosphors is analyzed using temperature-dependent spectroscopy. The emission spectra of NCSO: Bi3+, Eu3+ are consistent with the absorption spectra of chlorophyll a, chlorophyll b, phytochrome PR, and phytochrome PFR. These results indicate that the obtained phosphors exhibit significant potential for inducing plant growth.