Starting out as a manufacturer of water mills, in the late 19th century Jean Pequignot Peugeot expanded his business opening a steel works. From 1882 one of the primary products of this works was bicycles, sold as Cycles Peugeot. 
By the start of the 20th century Peugeot was split between Automobiles Peugeot and Cycles Peugeot - the cycles business was the more successful until the 1950s, when European interest in cycling as a means of transportation virtually disappeared. At this point bicycle production was cut and efforts focused on production for the automotive industry. 
Towards the end of the 1960s there was a resurgence in cycling interest and Peugeot gradually increased its production of sport, racing, and touring road bicycles. 
This sign would have been a part of Peugeot's renewed focus on their cycling division. 

 

Usually these tin (rather than enamel) signs are litho printed, though I wonder whether this example is screen printed or even stencilled. It's unusually, but endearingly, crude in it's creation with wobbly border edges and even paint runs in the top corner. I would speculate that the sign was created on license by a smaller manufacturer. It's almost certainly French and is likely to date to the 1960s / early '70s. It's a 'flange' sign - designed to be wall mounted and stick out at a 90 degree angle - clearly visible to passers by. 

 

The sign has aged well, there's some surface scratching, some light corrosion and some paint loss on the lower corner but this all adds to the character of the piece with out detracting from the legibility or impact of it. 

 

The sign measures 55cm wide x 40cm high and the flange is 5cm deep.

 

S/N: #2465