There was a long article about this in the Deutsche Waffenjournal (DWJ) of March 2010. The weapons used were (most likely) 7.65 mm Walther PPK pistols acquired by Poland in early 1939. Some pistols from this batch (with Polish acceptance stamps) came on the collectors' market from Russia in the 1990s - see picture. A NKVD major (allegedly) later bragged about killing 7,000 Poles with his Walther.
The origin of the 7.65 mm Geco ammunition as found at Katyn is not clear. Small amounts had been supplied to the USSR up to 1928, but with different headstamps. It could have been captured Polish ammunition, or from the Baltic States. Apparently Latvia bought several million rounds from Geco in 1938/39. As this Geco ammo was widely exported, as noted above, other sources are also possible.
The reason the NKVD used this particular calibre was most likely just that they wanted to use up nonstandard ammunition. Also, while the 7.65 mm Browning (.32 ACP) was/is not really powerful enough for combat use, it was adequate for this job.
German ammo at Katyn forest
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