PVC is flammable (or inflammable rather), and the gas is toxic, so be careful. Obviously it is higher than 100C, so hot water won't work. I don't remember exactly, but I think it is around 175C. Check the combustion temperature of PVC to make sure it is not that close.
I prefer to use heat gun or heating stripe for this purpose, since heating it in a furnace usually make the whole PVC piece too soft to hold the shape when you work on it. Be very careful if you decide to use flame!
I used heated oil in a tuna fish can. It did the trick much before the oil started to smoke. Prepare to mess up the first one unti you get the hang of it, but by varying the amount of time you keep it dip you can get it pretty hard, medium or really soft.
I have use a heat gun several times to flare the ends of PCV and CPVC. The biggest trick it to keep the heat gun far enough away so that it doesn't "tan" the fitting.
The heat guns that are made to heat PVC pipe to bend pipes should work on the fittings too.
I would just be careful to keep the the gun moving so that you don't melt the fitting. Keep turning the fitting and you'll be able to feel it when it starts to become plyable.