Photoreaction and photoinduced molecular reorientations in nanoscaled films of poly(methyl 4-(methacryloyloxy)cinnamate) (PMMCi) were investigated through two-dimensional (2D) correlation analyses of their infrared (IR) and ultraviolet (LTV) absorption spectra. In the PMMCi film the presence of three distinct chromophore types was evident: isolated trans-isomeric cinnamoyl moieties and parallel and end-to-end cinnamoyl aggregates. Their photoinduced reorientations take place in the following sequence: isolated trans isomeric chromophores --> parallel chromophore aggregates --> end-to-end chromophore aggregates. It turns out that they react photochemically at different rates. The PMMCi polymer molecules were found to undergo both photoisomerization and photodimerization upon LTV irradiation, with the trans-cis isomerization of the isolated trans isomeric cinnamoyl moieties occurring more rapidly than the photodimerization of the cinnamoyl aggregates. Of the photodimerization processes, the reorientation of the parallel cinnamoyl aggregates precedes that of the end-to-end cinnamoyl aggregates. The isolated chromophores may partly involve in the photodimerization, but its fraction is expected small because of the film in a confined geometry. The cinnamoyl moiety was found to be present as two rotational conformers, trans-s-trans and trans-s-cis conformers. Upon UV irradiation, the trans-s-trans conformer changes before the trans-s-cis conformer. The cinnamoyl moieties undergo a cooperative reorientation with the methacryloyloxy units during photoreaction. The photoinduced molecular reorientations occur in the following sequence: trans isomer --> phenyl ring --> trans-s-trans conformer --> trans-s-cis conformer photodimer.