Urban region profiling from web-sourced data is of utmost importance for urban planning and sustainable development. We are witnessing a rising trend of LLMs for various fields, especially dealing with multi-modal data research such as vision-language learning, where the text modality serves as a supplement information for the image. Since textual modality has never been introduced into modality combinations in urban region profiling, we aim to answer two fundamental questions in this paper: i) Can textual modality enhance urban region profiling? ii) and if so, in what ways and with regard to which aspects? To answer the questions, we leverage the power of Large Language Models (LLMs) and introduce the first-ever LLM-enhanced framework that integrates the knowledge of textual modality into urban imagery profiling, named LLM-enhanced Urban Region Profiling with Contrastive Language-Image Pretraining (UrbanCLIP). Specifically, it first generates a detailed textual description for each satellite image by an open-source Image-to-Text LLM. Then, the model is trained on the image-text pairs, seamlessly unifying natural language supervision for urban visual representation learning, jointly with contrastive loss and language modeling loss. Results on predicting three urban indicators in four major Chinese metropolises demonstrate its superior performance, with an average improvement of 6.1% on R^2 compared to the state-of-the-art methods. Our code and the image-language dataset will be released upon paper notification.