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Rotten potatoes have a distinctive unpleasant odour, and I can't find any definitive answer as to what the chemical involved is. My first guess was that it was putrescine and other polyamines---but the smell of putrefying potatoes actually comes from methyl mercaptan, dimethyl sulfide, and dimethyl trisulfide. Methyl mercaptan ($\rm CH_3SH$) has an odor described as "rotting cabbage" by ATDSR; it's one of the major contributors to the smell of farts (oh, sorry, "flatus" if we're being polite).
Dimethyl sulfide ($\rm (CH_3)_2S$) is responsible for the smell of the sea (in low concentrations); it too has a cabbagy smell.

The gases produced by rotting potatoes are quite toxic (see Rotting potatoes in basement kill four members of Russian family). It is a combination of potato and a fungus or bacterium that causes a potato to rot and produce the offensive odor.
Not only is the odor of rotting potatoes extremely unpleasant, but it has been reported to be lethal. Most of the headspace chromatography studies I found dealt with early detection of disease organisms in infected potatoes, rather than potatoes in full putrefaction mode.

You'll also find many references to solanine poisoning from potatoes; solanine is a toxic glycoalkaloid, is nonvolatile, and has nothing at all to do with the foul smell and toxic gas produced by putrid potatoes. Everything living contains putrescine, more in animals, less in plants; but not everything dead smells like putrescine.

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