Distributed representations of words (aka word embedding) have proven helpful in solving natural language processing (NLP) tasks. Training distributed representations of words with neural networks has lately been a major focus of researchers in the field. Recent work on word embedding, the Continuous Bag-of-Words (CBOW) model and the Continuous Skip-gram (Skip-gram) model, have produced particularly impressive results, significantly speeding up the training process to enable word representation learning from largescale data. However, both CBOW and Skip-gram do not pay enough attention to word proximity in terms of model or word ambiguity in terms of linguistics. In this paper, we propose Proximity-Ambiguity Sensitive (PAS) models (i.e. PAS CBOW and PAS Skip-gram) to produce high quality distributed representations of words considering both word proximity and ambiguity. From the model perspective, we introduce proximity weights as parameters to be learned in PAS CBOWand used in PAS Skip-gram. By better modeling word proximity, we reveal the strength of pooling-structured neural networks in word representation learning. The proximitysensitive pooling layer can also be applied to other neural network applications that employ pooling layers. From the linguistics perspective, we train multiple representation vectors per word. Each representation vector corresponds to a particular group of POS tags of the word. By using PAS models, we achieved a 16.9% increase in accuracy over state-of-theart models.