Availability of conjugated polymer thin films with precisely defined molecular structure and chain alignment is important for increasing efficiency and improving the performance of thin-film based polymer devices, such as organic light-emitting diodes, photovoltaics, and chemo- and biosensory materials. A promising approach is controlled surface-initiated polymerization that can produce thick films with uniform bulk morphology and structural organization. Herein, we present a series of poly(p-phenylene ethynylene) thin films prepared by stepwise surface-initiated polymerization. In addition to experimental simplicity and reproducibility of the preparation, and a broad variety of compatible building blocks, this method requires low material consumption and no purification for the final bulk thin films. The stepwise surface-initiated polymerization yields dense films of covalently immobilized polymer chains with precisely controlled molecular structure and organization. For thin films prepared in this study, their surface morphology and mesoscale organization were studied by atomic force microscopy and neutron reflectometry; and their photophysical and electrochemical properties will be detailed in the presentation.