We demonstrate the synthesis of biogenic supported silver spiked star architectures and their application to increase the electromagnetic field intensity at its tips that enhance plasmoncoupled emission. Tecoma stans floral extract has been used to synthesize silver nanocubes and spiked stars. We observe ∼445-fold and ∼680-fold enhancements in spacer and cavity configurations, respectively, in the SPCE platform. The hotspot intensity and Purcell factor are evaluated by carrying out finite-difference time-domain (FDTD) simulations. Time-based studies are presented to modulate the sharpness of the edges wherein an increase in the tip sharpness with the increase in reaction time up to 5 h is observed. The unique morphology of the silver architectures allowed us to utilize them in biosensing application. A SPCE-based fluoroimmunoassay was performed, achieving a 1.9 pg/mL limit of detection of TNF-α cytokine. This combination of anisotropic architectures, SPCE and immunoassay prove to be a powerful platform for the ultrasensitive detection of biomarkers in surface-bound assays.