The one- and two-photon photoluminescence as well as the Raman scattering of poly{[4,4-bis(alkyl-cydopenta(2,1-b;3,4-b')-dithiophene)] -2,6-diyl-alt-(2,1,3-benzothiadiazole)-4,7-diy1}(PCPDTBT) thin films processed from different organic solvents are reported. Benefiting from a high optical resolution of down to 300 nm, we demonstrate a method that is able to determine the local morphologies even in individual micron-sized ordered polymer structures. Combining angle-resolved emission spectroscopy and polarization excitation spectroscopy, we study the local morphology dependent optical properties and the molecular orientations of PCPDTBT thin films. Two types of morphologies, namely dendritic spherulite and terrace-like structures, obtained in chlorobenzene (CB) solvent annealed PCPDTBT thin films are used as model systems. With the assistance of an analytical model, we can identify that the molecules in the terrace-like structure possess upright orientations and in the dendritic spherulite have a tilt angle of about 40 with respect to the substrate surface. Furthermore, polarized excitation Raman spectra indicate the fraction of local order to be around 40% on average for dendritic spherulite structures. For the terrace-like structure, even higher fractions of local order of on average 75% are deduced.