Methanol is ubiquitous in star-forming regions, and has recently been detected in a protoplanetary disk. Astrochemical models have shown that methanol photolysis contributes to complex organic chemistry in interstellar ices. While some methanol photolysis branching ratios have been measured, infrared condensed-phase measurements rely on assumptions about the chemistry, and mass spectrometric measurements cannot distinguish structural isomers. To address these challenges, we are using pure rotational spectroscopy to quantitatively probe the methanol photolysis products. We use a VUV laser to dissociate methanol in the throat of a supersonic expansion, and probe the products downstream after cooling is complete. We then use a rotational diagram analysis to determine the relative density of each product relative to methanol. We have detected the methoxy, hydroxymethyl, and formaldehyde photolysis products. We present here the experimental setup and the initial results and discuss these results in the context of interstellar chemistry.