You cannot access the broadcast of The CW or CWTV outside the US due to geo-restriction hassles. Therefore, you will have to use a VPN that offers a US IP address. You will have to mask your original IP address with an IP address of your desired country first, which will be in this case USA.
By doing so, you can download The CW app through Google Play Store on your Android device. You can start watching your favorite shows like Hart of Dixie, The Originals, and others once you have downloaded the app.