Yes, as long as there is riskless profit to be made, arbitrageurs will jump in and ensure that no such mispricing occurs. Arbitrage though doesn't work the way trade100 as mentioned, you cannot buy on BSE and sell on NSE. Check this question.
@Astro, yes demand and supply can move the price in one of the exchanges away from the price of the other. But it is the arbitrageurs who ensure that it doesn't stay that way for too long, actually in todays age such opportunities last for just a few seconds.
So if stock A was Rs 100 on NSE and Rs 105 on BSE. The person who has Stock A in his account, can sell on BSE at 105 and immediately buy back on NSE at 100 to make a riskless 5%. There will be so many people trying to do this that the opportunity even if it lasts might be for a few seconds. This ensures that there is never a big gap between NSE and BSE.