In the present paper, the photoemission temperature dependence of host/guest blends has been investigated. The polymers blend is composed by poly(n-alkyl metacrylate) (PnMA) as a host and poly [(9,9-dihexyl-9H-fluorene-2,7-diyl)-1,2-ethenediyl-1,4-phenylene-1,2-ethenediyl] (LaPPS16) as a guest. The PnMAs/LaPSS16 blends presented high homogeneity and photoemission temperature stability (T similar to 30-410 K). Moreover, the PnMA/LaPPS16 blends photoemission in function of sample temperature allowed access to the PnMA molecular relaxations temperatures. This was possible due to the strong interaction between the PnMA n-alkyl side groups and the LaPPS16 aliphatic groups. In addition, the blends films were characterized by Wide-angle X-ray Diffraction, optical absorbance, steady-state photoluminescence spectroscopy, Emission Ellipsometry, and Dynamic Mechanical Analysis. (C) 2016 Elsevier Ltd. All rights reserved.