If you are in UK and your wife is in India, then you'll have to travel to India and apply for EC from there if you wish to apply along with your wife.
Alternatively, you may apply here (in the UK) and, when granted, your wife can then apply for EC (in India) as dependent of PBS migrant.
When applying from within the UK, refer to
UKBA website. When applying from outside the UK, refer to
UKVisas website. Policy guidance is common, irrespective of where the application is being submitted. Read
Tier 1 (PSW) policy guidance and
Policy guidance on PBS dependents carefully.
regards