We report on Keck optical BVRI images and spectroscopy of the companion of the binary millisecond pulsar PSR J0218+4232. A faint bluish (V=24.2, B-V=0.25) counterpart is observed at the pulsar location. Spectra of this counterpart reveal Balmer lines which confirm that the companion is a Helium-core white dwarf. We find that the white dwarf has a temperature of Teff=8060+-150 K. Unfortunately, the spectra are of insufficient quality to put a strong constraint on the surface gravity, although the best fit is for low log g and hence low mass (~0.2 Msun), as expected. We compare predicted white dwarf cooling ages with the characteristic age of the pulsar and find similar values for white dwarf masses of 0.19 to 0.3 Msun. These masses would imply a distance of 2.5 to 4 kpc to the system. The spectroscopic observations also enable us to estimate the mass ratio between the white dwarf and the pulsar. We find q=7.5+-2.4, which is consistent with the current knowledge of white dwarf companions to millisecond pulsars.