Knowing nothing short of a win today would see them through to the knockout stages, Congo DR came flying out of the traps and took the lead through Dieumerci Mbokani's penalty. But Samassa, starting in place of Cheick Diabate, equalised in the 13th minute and while both sides had chances to win the match, they had to settle for a draw as Mali sealed their passage from Group B alongside Ghana, who beat Niger 3-0.
But that looked a long way off when Congo DR attacked from the first whistle, with former Newcastle United and Portsmouth forward Lomana LuaLua striking against the base of the post inside the first 30 seconds.
The Congolese continued to attack and they were awarded a penalty in the third minute when midfielder Yves Ilunga was tripped by Mohamed Sissoko in the area, with Mbokani hammering into the top corner from the spot. It was just the start Claude Le Roy had wanted, with the coach bemoaning their goalless draw against Niger last time out.
But the goal spurred Mali into action and they equalised with their first opportunity of the match. Adama Tamboura's cross from the left side of the penalty area was slotted home from close range by Samassa in the 14th minute.
They then had an excellent opportunity to take the lead midway through the half but Adama Coulibaly headed wide from an inswinging corner by Seydou Keita, whose cross to West Ham striker Modibo Maiga shortly before the interval was nodded over.
It had been a real battle and with both teams capable of qualification, no-one from either side wanted to make a costly mistake. But Mali were holding firm, with Samba Diakite, Keita and Sissoko excelling in midfield to snuff out any openings DR Congo had.
Mbokani headed meekly wide just after the hour mark but at the other end, Robert Kidiaba's weak parry from Samassa's 20-yard effort only just went wide of the goal and spared Congo DR's blushes.
Mali goalkeeper Mamadou Samassa made a fantastic save from Youssouf Mulumbu's effort from just outside the area to keep the scores level.
But Mali showed they were not content to hang on for a draw, with substitute Diabate running through on goal and rounding Kidiaba but seeing his strike from a narrow angle hit the outside of a post.
It mattered little, however, as Les Aigles hung on in the closing stages to send DR Congo, who had drawn all three group matches, crashing out.