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I have a good CV and want to pursue an LLM after my degree, but want a law firm job offer as a back up.

Does anyone know any Indian law firms that allow PPO holders to defer (and maybe even later on cancel) their offers in case they get selected for an LLM?
Unlikely you will be able to do so for two reasons. One, LLM being zero value add for a law firm and two, now that you will end up doing the LLM any way, you are likely to move abroad.
I do know of a few people who got a PPO, then got an LLM offer from Ivys/OxBridge, spoke to the firm and deferred the joining date by a year. Definitely possible. But none of them were from T1 firms.