Thick-film phosphor-in-glasses (PiGs) were fabricated via a screen-printing method with various phosphor layer structures, to compose a white light emitting diode (LED). Green (Lu3Al5O12:Ce3+) and red (CaAlSiN3:Eu2+) phosphors were mixed, layered, and patterned on a glass substrate. The chromaticity of each structured PiG was tuned to achieve a white LED by varying phosphor content and thickness. The emission spectra and the related various color conversion properties, including color coordinates, correlated color temperature (CCT), color rendering index (CRI), luminous efficacy (LE) and the color gamut of the mounted PiGs with different phosphor layer structures were examined and compared. Time-resolved photoluminescence (TRPL) measurements of the white LEDs with various phosphor layer structural designs were also obtained and compared. It was observed that spectral variation depended on the PiG layer structure. A proper PiG layer structural design was discussed for practical applications.