In this work we investigate the work function of gallium phosphide nanowires by the means of frequency-modulated Kelvin probe force microscopy. Polytypic wurtzite/zinc blende nanowires were synthesized via self-catalytic molecular beam epitaxy. Mixed crystal phase was achieved by controlling the catalytic droplet contact angle and confirmed via transmission electron microscopy and Raman spectroscopy. Kelvin probe study showed a contrast between the work function of (110) zinc blende and (1120) wurtzite gallium phosphide: ϕZB = 4.28 eV and ϕWZ = 4.2 eV. Also, it was shown that sub-monolayer arsenic shell increases the work function up to 4.75 eV. Thus, two mechanisms for work function adjustment in the range 4.2-4.75 eV are shown. The results are important for optimization of Schottky barriers in nanowire-based devices.