X-ray spectrum plays a very important role in dual energy computed tomography (DECT) reconstruction. Because it is difficult to measure x-ray spectrum directly in practice, efforts have been devoted into spectrum estimation by using transmission measurements. These measurement methods are independent of the image reconstruction, which bring extra cost and are time consuming. Furthermore, the estimated spectrum mismatch would degrade the quality of the reconstructed images. In this paper, we propose a spectrum estimation-guided iterative reconstruction algorithm for DECT which aims to simultaneously recover the spectrum and reconstruct the image. The proposed algorithm is formulated as an optimization framework combining spectrum estimation based on model spectra representation, image reconstruction, and regularization for noise suppression. To resolve the multi-variable optimization problem of simultaneously obtaining the spectra and images, we introduce the block coordinate descent (BCD) method into the optimization iteration. Both the numerical simulations and physical phantom experiments are performed to verify and evaluate the proposed method. The experimental results validate the accuracy of the estimated spectra and reconstructed images under different noise levels. The proposed method obtains a better image quality compared with the reconstructed images from the known exact spectra and is robust in noisy data applications.