The first Europeans to travel up the river, Etienne Brule (1610), and Samuel de Champlain (1615) did so in the canoes of their First Nation guides.
For some 200 years thereafter, the Mattawa River formed part of the important water route leading from Montreal west to Lake Superior. It was the primary access to the vast Canadian interior in the days of the fur trade.
During the early days of logging in the area, the Mattawa River was used to float logs downstream to mills.
The arrival of the railroad to Papineau-Cameron in 1881 was the beginning of the end of the Papineau-Cameron Township as an important transportation link. Since 1970, much of the river has been protected as the Mattawa River Provincial Park, and remains a premier recreational paddling route.
Each July recreational paddlers challenge the rivers entire 64km length from North Bay to Mattawa, in the one day Mattawa River Canoe Race.
The river can be broken up into various day and multi day paddling trips, by either canoe or kayak.