Low Temperature Co-fired Ceramic (LTCC) is an important technology in high frequency electronics applications and enables the fabrication of several ceramic layers with cavities, channel structures and micro-vias for embedded passive and active components. Typically, laser cutting combined with screen printing technology are used to form metallized cavities and micro-vias on green state LTCC. However, in this study, the excimer laser (248 nm wavelength) machining process combined with electroless copper plating was successfully employed to create selectively metallized channel structures on fired LTCC substrates. Dry film photoresist was used within the process to guide the activation of the laser machined surface with Sn/Pd catalyst prior to electroless copper deposition. The effect of different laser parameters were investigated and machined channels were characterized for their maximum depth and surface roughness. It was found that there was a significant correlation between the laser machining parameters and the channel characteristics which also affected the subsequent electroless copper plating and its electrical resistance.