Anti-Stokes photoinduced electrochemiluminescence (PECL) converts infrared photons to visible photons and is usually triggered at a narrow band gap-protected photoanode. Here, we report the first example of PECL with the model [Ru(bpy)3]2+/benzoyl peroxide system at a bare p-type Si photocathode. The reported PECL system, which allows a notable decrease of the cathodic potential required for ECL generation, should open new opportunities for imaging and light-addressable devices.