Ethanol decomposition on Pd(110) is comprehensively investigated using self-consistent periodic density functional theory. Geometries and energies for all the intermediates involved are analyzed, and the decomposition network is mapped out to illustrate the reaction mechanism. On Pd(110), the most stable adsorption of the involved species tends to follow the gas-phase bond order rules, wherein C is tetravalent and O is divalent with the missing H atoms replaced by metal atoms. The most likely decomposition pathway of ethanol on Pd(110) is CH₃CH₂OH → CH₃CH₂O → CH₃CHO → CH₃CO → CH₃ + CO → CO + H + CH₄ + C, in which the initial dehydrogenation is the rate-limited step. No C–O scission pathway is identified. Comparing with ethanol decomposition on Pd(111) [Langmuir, 2010, 26, 1879–1888], Pd(110) characterizes relatively high activity and different selectivity. Two crucial factors controlling the variations of reactivity and selectivity from Pd(111) to Pd(110), i.e., the local electronic effect of the metals and the geometrical effect of the relevant transition states, are identified. Four distinct Brønsted-Evans-Polanyi (BEP) relations are identified for the three types of bond scission (C–H, C–O, and C–C) if we consider Pd(111) and Pd(110) as a whole, one for C–H bond scission, one for C–O bond scission, and two for C–C bond scission.