Plasma-enhanced chemical vapor deposition (PECVD) is a valuable technique for deposition of polymeric materials with wide ranging applications, including micropatterns for fabrication of multianalyte biosensors, diagnostic tests, DNA microchips, and genomic arrays. One ongoing issue with PECVD processes is controlling and tailoring the molecular level chemistry, both in the gas-phase and at the gas-surface interface such that predictable and reproducible film chemistries can be created. One method for controlling the overall deposition is to use pulsed, downstream or remote deposition processes. Moreover, understanding surface interactions of plasma species provides critical molecular level information about PECVD processes. The imaging of radicals interacting with surfaces (IRIS) technique examines interactions of radicals during plasma deposition using laser-induced fluorescence (LIF) to provide spatially-resolved 2D images of radical species involved in film formation. IRIS allows for direct determination of radical-surface interactions during plasma processing. IRIS data for species in plasma polymerization and plasma modification systems will be presented, along with addition film and gas-phase composition data. IRIS results that will be discussed include data on fluorocarbon radicals (CF and CF@sub 2@), main group hydrides (SiH, OH, NH, and CH), and nitrogen-containing molecules (NH, NH@sub 2@, CN) in relationship to various plasma polymerization systems of interest to the microelectronics and coating industries. Correlation of gas-phase data, surface analysis, and plasma-surface interface reactions will also be presented to provide more comprehensive mechanisms for overall plasma polymerization processes. Examples will also be provided from polymer film and fiber modification systems.