No, you can't decide whether to call Bcast or Recv on the basis of a probe call.
A MPI_Bcast call is a collective operation -- all MPI tasks must participate. As a result, these are not like point to point communication; they make use of the fact that all processes are involved to make higher-order optimizations.
Because the collective operations imply so much synchronization, it just doesn't make sense to allow other tasks to check to see whether they should start participating in a collective; it's something which has to be built into the logic of a program.
The root process' role in a broadcast is not like a Send; it can't, in general, just call MPI_Bcast and then proceed. The implementation will almost certainly block until some other number of processes have participated in the broadcast; and
The other process' role in a broadcast is not like receiving a message; in general it will be both receiving and sending information. So participating in a broadcast is different from making a simple Recv call.
So Probe won't work; the documentation for MPI_Probe is fairly clear that it returns information about what would happen upon the next MPI_Recv, and Recv is a different operation than Bcast.
You may be able to get some of what you want in MPI 3.0, which is being finalized now, which allows for nonblocking collectives -- eg, MPI_Ibcast. In that case you could start the Broadcast and call MPI_Test to check on the status of the request. However, even here, everyone would need to call the MPI_Ibcast first; this just allows easier interleaving of collective and point-to-point communication.