Context. Within the framework of the HERM33ES key program, we are studying the star forming interstellar medium in the nearby, metal-poor spiral galaxy M33, exploiting the high resolution and sensitivity of Herschel. Aims. We use PACS and SPIRE maps at 100, 160, 250, 350, and 500 mu m wavelength, to study the variation of the spectral energy distributions (SEDs) with galacto-centric distance. Methods. Detailed SED modeling is performed using azimuthally averaged fluxes in elliptical rings of 2 kpc width, out to 8 kpc galacto-centric distance. Simple isothermal and two-component grey body models, with fixed dust emissivity index, are fitted to the SEDs between 24 mu m and 500 mu m using also MIPS/Spitzer data, to derive first estimates of th...