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There is a Hill Climbing mode that starts the gas engine up earlier if you have a long mountain pass to go up that the gas engine might not be powerful enough to handle on it's own.
There are a lot of improvements that could be made to the Volt, but they wanted it to be all electric for the first 32 miles, when the battery is down to 20% (what they call empty) the gas engine starts up and can drive the wheels while bypassing the motor/generator, just like the Prius does (yes, the volt and plug in Prius drive trains are really similar to each other, but different enough that they don't use the same patents), otherwise it would have made sense for them to tune the gasoline engine to turn at a single set speed because at that point they could have squeezed more MPG out of it but they wanted it to sound like a normal gasoline car when it is running on gasoline, with engine revving and so on.
So the short answer to your question is yes, if you know you are going to run the battery dead it would most likely give you better over all mileage/range to have the gasoline engine start up while cruising down the highway.
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