Electrolysis of calcium hydroxide in glycerol
Calcium hydroxide is probably slightly soluble in glycerine due to tight chelation of Ca++ ion by the three hydroxyls of (probably 2) glycerine(s). But the hydroxyls will be present too, and on hydrolysis, will yield O2 plus H2O.

But beyond that, imagine you produce some calcium metal: it will be in glycerine, which has hydroxyl groups that will react with the Ca to produce H2. It could be a competition where some conditions allow production of measurable amounts of Ca metal, but it doesn't look promising. PEG 400 (polyethylene glycol with a mw of 400) has been used as a solubility enhancer for Ca(OH)2 (similar to glycerine), but has many fewer hydroxyls, and might do the job better. https://www.mdpi.com › pdf yields a pdf with more information.

Glycerine and PEG seem to be used to increase solubility of Ca(OH)2 in water rather than in the other solvent alone. I suspect increased viscosity is an issue.

Another way to get some calcium would be to use mercury as the cathode; then calcium will deposit and amalgamate (I'm pretty sure. I've done it with sodium and ammonium, but not with calcium.).