We present near-infrared multi-object spectroscopy and JHKs imaging of the massive stellar content of the Galactic star-forming region W3 Main, obtained with LUCI at the Large Binocular Telescope. We confirm 15 OB stars in W3 Main and derive spectral types between O5V and B4V from their absorption line spectra. Three massive Young Stellar Objects are identified by their emission line spectra and near-infrared excess. The color-color diagram of the detected sources allows a detailed investigation of the slope of the near-infrared extinction law towards W3 Main. Analysis of the Hertzsprung Russell diagram suggests that the Nishiyama extinction law fits the stellar population of W3 Main best (E(J-H)/E(H-Ks) = 1.76 and R_(Ks) = 1.44). From our spectrophotometric analysis of the massive stars and the nature of their surrounding HII regions we derive the evolutionary sequence of W3 Main and we find evidence of an age spread of at least 2-3 Myr. While the most massive star (IRS2) is already evolved, indications for high-mass pre-main-sequence evolution is found for another star (IRS N1), deeply embedded in an ultra compact HII region, in line with the different evolutionary phases observed in the corresponding HII regions. We derive a stellar mass of W3 Main of (4 +- 1) 10^3 Msun, by extrapolating from the number of OB stars using a Kroupa IMF and correcting for our spectroscopic incompleteness. We have detected the photospheres of OB stars from the more evolved diffuse HII region to the much younger UCHII regions, suggesting that these stars have finished their formation and cleared away their circumstellar disks very fast. Only in the hyper-compact HII region (IRS5), the early type stars seem to be still surrounded by circumstellar material.
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