Ministry spokeswoman Irina Andrianova said it had been flying from Moscow to Smolensk, but had no details on the identities of those killed.
Smolensk regional governor Sergei Antufiev told Russian TV that no-one had survived.
"As it was preparing for landing, the Polish president's aircraft did not make it to the landing strip," he said.
"According to preliminary reports, it got caught up in the tops of trees, fell to the ground and broke up into pieces. There are no survivors in that crash.
"We are clarifying how many people there were in the [Polish] delegation. According to preliminary reports, 85 members of the delegation and the crew."
