Three ways you can disable skip shift:
1) On 89-95, just unplug the skip shift solenoid on the side of the trans
2) On 96-13, install a skip shift eliminator, available from CAC sponsor Zip Products and other aftermarket sources.
3) on 89-13 get an aftermarket calibration which has the skip shift function disabled.
Also, you can avoid skip shift without spending any money if you learn to drive though it. Most people who get skip shift regularly, are very easy drivers (like they have a goldfish bowl on the seat) and always short shift out of first. That's really not the way to drive a Corvette. If you accelerate just a tiny bit more aggressively and hold the 1-2 shift a little longer, like a sports car should be driven; you'll reduce the number of skip shift intrusions to almost nothing.
On the three Vettes I have with that feature, only one, a 95, has it disabled in the calibration and I really didn't ask for it to be done, the guy just did it. The other two, an '04 and a '12, have skip shift functional but it rarely enables. If it does, no biggie, I just shift to fourth. If I'm driving in a manner that allows skip shift to enable, the extra gas mileage won't hurt.
Lastly, a little history...skip shift has nothing to do with exhaust emissions. It was developed for the late C4 six-speed as a way to gain fuel economy and meet the CAFE standards of the day. It's still used mainly for that reason on Corvette and other V8 cars with manuals. A secondary benefit was that it allowed the Corvette to meet the pass-by noise standard in California and other states which observe that standard. Up until the advent of the C6 dual-mode exhaust, that was another important reason for skip shift. In short, the test required the car to start out in first, shift to the next highest gear then accelerate at WOT past the microphones. A smart Corvette engineer bamboozled the California Highway Patrol into accepting the idea that since skip shift made fourth the next highest gear, they could pass by the mics at WOT, low rpm in fourth rather than high-rpm in second.
Pretty sharp thinking if you ask me.
I appreciate the much-maligned skip shift because it's allowed us to have high-performance Corvettes without guzzler (well...other than C6 ZR-1s) and to have less restrictive exhausts.