I needed a vector file of power transmission lines within my study site in Central India. But since there wasn't any, I decided to map the power transmission lines in Google Earth. Is there any way where I can ascertain how accurate this method is?
That depend on the scale, but Google Earth can be geo-referenced and used. Many people has been using it, especially when it comes to larger scales. Yes of cause you can use it but you have to make sure you have another image or map for guidance.
If you extracted the transmission line correctly, then the accuracy will be according to the image resolution. This rule suppose that the image (source) is correctly georeferenced. Much of Google Earth high resolution-imagery is provided by DigitalGlobe (50 cm maximum resolution).