In this paper, the electrochemiluminescence (ECL) of calixarene carboxylic acid coated porous Si (PS) is reported. Electrochemiluminescence is observed from the anodic oxidation of calixarene-coated porous Si in an electrolyte containing 1.0 M H2SO4 These calixarene carboxylic acid derivatives coated onto the porous Si surface affect both the duration and efficiency of the light emission. Electrochemiluminescence can be generated for longer periods of time for these coated porous Si junctions relative to untreated porous Si, ranging from up to 3 h for calix[4]arene-coated porous Si to about 50 min for the calix[n]arene (it = 5, 7, 8) derivatives. This improved duration of electrochemiluminescence comes at the cost of quantum efficiency; for calix[8]arene-coated PS it is 0.0015%, while for calix[4]arene-coated porous Si, <0.001%. The electrochemiluminescence peak maximum is red-shifted beyond 700 nm with continued bias. These observations are attributed to packing differences between different calixarene carboxylic acid derivatives as thin films and subsequent bias-induced Si nanoparticle oxidation in the porous matrix.