We present a bottom-up approach for the construction of tunable functional defects in colloidal photonic crystals (CPCs). These structures incorporate polyelectrolyte multilayer (PEM) planar defects embedded in silica CPCs through a combination of evaporation induced self-assembly and microcontact transfer printing. We show how the enormous chemical diversity inherent to PEMs can be harnessed to create chemically active defect structures responsive to solvent vapor pressures, light, temperature as well as redox cycling. A sharp transmission state within the photonic stopband, induced by the PEM defect, can be precisely, reproducibly and in some cases reversibly tuned by these external stimuli. These materials could find numerous applications as optically monitored chemical sensors, adjustable notch filters and CPC-based tunable laser sources.