A reduced order model (ROM) is proposed for accurate prediction of electrochemical and thermal response of lithium ion cells. The order reduction is carried on the coupled partial differential equations (PDE) of the electrochemical thermal model by consistent volume averaging of local heat generation and spatial temperature variation. The model is validated with experimental data for temperatures ranging from 253 K–333 K. It is seen that modification of ROM to account for low electronic conductivity results in accurate voltage estimation of cells with lithium nickel cobalt aluminium oxide (LNCO) cathodes. A detailed parametric sensitivity to operating conditions is provided. The utility of ROM for on-board state estimation is demonstrated by applying to realistic drive cycle protocols such as the Hybrid Pulse Power Characterization (HPPC) and the Urban Dynamometer Driving Schedule (UDDS) data. The electrochemical structure of ROM enables identification of controlling processes, and analysis of HPPC results reveal that Ohmic drop of cathode is controlling at high rates and the electrolyte potential during rest phase. Based on accurate voltage prediction, computational speed and physical insights, it can be concluded that the proposed ROM is an adequate state estimation and a cell design tool.